JP2021176697A - Decorative sheet - Google Patents

Abstract

To provide a decorative sheet capable of applying excellent design feeling and touch feeling owing to a concave-convex shape to a resin molded product.SOLUTION: A decorative sheet is formed by laminating at least a base material layer, a surface layer which is formed by a cured matter of a curable resin composition and has a concave-convex shape, and a peelable thermoplastic resin film layer in this order.SELECTED DRAWING: None

Description

The present invention relates to a decorative sheet capable of imparting an excellent design feeling and a feeling of touch due to the uneven shape.

Decorative resin molded products in which a decorative sheet is laminated on the surface of the resin molded product are used for vehicle interior parts, building material interior materials, home appliance housings, and the like. Further, in recent years, with the diversification of consumer needs, decorative resin molded products having various designs are required. In order to meet such diversifying consumer needs, it is desired to develop a decorative resin molded product having an uneven shape on the surface and having a good design feeling as well as a good touch.

Conventionally, in the production of decorative resin molded products, a molding method in which a decorative sheet to which a design property has been given in advance is integrated with resin by injection molding has been used, and a decorative resin molded product having an uneven shape is formed. A decorative sheet having an uneven shape on the surface is used in the production of the above.

However, when a decorative resin molded product is manufactured using a decorative sheet having an uneven shape, the uneven shape is deformed by heat or pressure when the decorative sheet is subjected to injection molding or pre-molding (vacuum forming) prior to the injection molding. Since the decorative sheet is formed or disappears, the decorative sheet after injection molding cannot maintain the initial uneven shape, and there is a drawback that the design feeling and the feel feeling due to the uneven shape cannot be sufficiently imparted.

In order to overcome such drawbacks, a cushion layer made of a thermoplastic resin is laminated on the surface of a decorative sheet in which irregularities are formed by embossing on a thermoplastic base sheet by extrusion molding or a hot melt coating method. A method of suppressing deformation or disappearance of an uneven shape that occurs during vacuum forming or injection molding and removing the cushion layer after injection molding has been reported (see, for example, Patent Document 1).

However, in the method disclosed in Patent Document 1, the cushion layer provided for suppressing the deformation or disappearance of the uneven shape is formed by extrusion molding of a thermoplastic resin or a hot melt coating method, and thus melted thermoplasticity. There is a problem that the fine uneven shape on the surface of the thermoplastic substrate sheet is easily deformed or disappears due to the heat of the resin.

Japanese Unexamined Patent Publication No. 2008-137216

An object of the present invention is to provide a decorative sheet capable of imparting an excellent design feeling and a touch feeling due to an uneven shape to a resin molded product. Another object of the present invention is to provide a decorative resin molded product using the decorative sheet and a method for producing the same.

The present inventors have conducted diligent studies to solve the above problems. As a result, at least a decorative sheet formed by laminating a base material layer, a surface layer formed of a cured product of a curable resin composition and having an uneven shape, and a removable thermoplastic resin film layer in this order is obtained. It has been found that the removable thermoplastic resin film layer can effectively protect the uneven shape of the surface layer formed by the cured product of the curable resin composition. By using the decorative sheet, deformation and disappearance of the uneven shape that occurs during vacuum forming or injection molding can be suppressed, and an excellent design feeling and feel due to the uneven shape can be imparted to the decorative resin molded product. I found. The first invention of the present invention has been completed by further studying based on such findings.

That is, the first invention provides the invention of the following aspects.
Item 1. A decorative sheet in which at least a base material layer, a surface layer formed of a cured product of a curable resin composition and having an uneven shape, and a removable thermoplastic resin film layer are laminated in this order.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the surface layer is formed of a cured product of an ionizing radiation curable resin composition.
Item 3. Item 2. The decorative sheet according to Item 1 or 2, wherein the thermoplastic resin film layer contains an amorphous polyester resin.
Item 4. Item 3. The decorative sheet according to any one of Items 1 to 3, wherein the thermoplastic resin film layer is laminated on the uneven shape of the surface layer by extrusion molding or thermal lamination.
Item 5. Item 2. The decorative sheet according to any one of Items 1 to 4, wherein the thermoplastic resin film layer fills the concave-convex concave portion of the surface layer.
Item 6. Item 2. The decorative sheet according to any one of Items 1 to 5, wherein an adhesive layer is laminated between the surface layer and the thermoplastic resin film layer.
Item 7. Item 2. The decorative sheet according to any one of Items 1 to 6, wherein a primer layer is laminated directly below the surface layer.
Item 8. Item 2. The decorative sheet according to any one of Items 1 to 7, wherein a pattern layer is laminated between the base material layer and the surface layer.
Item 9. Item 2. The item 1 to 8, wherein the uneven shape of the surface layer is formed by a partially provided convex portion and a concave portion in which the lower layer of the surface layer is exposed between the convex portions. Decorative sheet.
Item 10. Item 2. The decorative sheet according to any one of Items 1 to 9, wherein the surface layer has a thickness of 0.01 to 30 μm.
Item 11. The first step of forming a laminated body having a concavo-convex shape and having a surface layer formed of a cured product of a curable resin composition laminated on the base material layer.
A second step of laminating a peelable thermoplastic resin film layer on the surface layer of the laminate obtained in the first step, and
A method of manufacturing a decorative sheet.
Item 12. Item 2. The method for producing a decorative sheet according to Item 11, wherein the thermoplastic resin film layer contains an amorphous polyester resin.
Item 13. Item 2. The method for producing a decorative sheet according to Item 11, wherein the second step comprises the following steps.
A step of laminating the peelable thermoplastic resin film layer on the surface layer by extrusion molding or thermal laminating so as to fill the concave-convex concave portions of the surface layer.
Item 14. Item 2. The method for producing a decorative sheet according to Item 11, wherein the second step comprises the following steps.
A step of laminating the adhesive layer by applying a resin composition on the surface layer and filling the concave-convex concave portions of the surface layer.
A step of forming the peelable thermoplastic resin film layer on the adhesive layer.
Item 15. At least, a heat formed by laminating a molding resin layer, a base material layer, a surface layer formed of a cured product of a curable resin composition and having an uneven shape, and a removable thermoplastic resin film layer in this order. Decorative resin molded product with a plastic resin film layer.
Item 16. Item 2. A method for producing a decorative resin molded product with a thermoplastic resin film layer, comprising a step of laminating a molding resin layer by injecting a resin onto the base material layer side of the decorative sheet according to any one of Items 1 to 10. ..
Item 17. Item 15. A method for producing a decorative resin molded product, comprising a step of peeling the thermoplastic resin film layer from the decorative resin molded product with the thermoplastic resin film layer according to Item 15.

In addition, the present inventors have conducted further diligent studies in order to solve the above-mentioned problems. As a result, at least a surface layer having a concavo-convex shape and a peelable concavo-convex protective layer are laminated, and the concavo-convex protective layer is an adhesive layer that fills the concavo-convex concave portion of the surface layer in order from the surface layer side. , It has been found that the decorative sheet provided with the release film layer can effectively protect the uneven shape of the surface layer by the uneven protective layer. By using the decorative sheet, deformation and disappearance of the uneven shape that occurs during vacuum forming or injection molding can be suppressed, and an excellent design feeling and feel due to the uneven shape can be imparted to the decorative resin molded product. I found. The second invention of the present invention has been completed by further studying based on such findings.

That is, the second invention provides the invention of the following aspects.
Item 18. At least, a surface layer having a concavo-convex shape and a peelable concavo-convex protective layer are laminated.
The concavo-convex protective layer is a decorative sheet including an adhesive layer that fills the concavo-convex recesses of the surface layer and a release film layer in this order from the surface layer side.
Item 19. Item 2. The decorative sheet according to Item 18, wherein the adhesive layer is formed of a cured product of a curable resin.
Item 20. The uneven protective layer includes a release layer, an adhesive layer, and a release film layer in this order from the surface layer side.
Item 18. The decorative sheet according to Item 18 or 19, wherein the release layer and the adhesive layer fill the concave-convex concave portions of the surface layer.
Item 21. Item 2. The decorative sheet according to any one of Items 18 to 20, wherein the release layer is formed of a cured product of an ionizing radiation curable resin composition.
Item 22. Item 2. The decorative sheet according to any one of Items 18 to 21, wherein the surface layer is formed of a cured product of a curable resin composition or a resin film.
Item 23. Item 2. The decorative sheet according to any one of Items 18 to 22, wherein a primer layer is laminated immediately below the surface layer.
Item 24. Item 2. The decorative sheet according to any one of Items 18 to 23, wherein a pattern layer is laminated on the side of the surface layer opposite to the uneven protection layer.
Item 25. The first step of preparing a surface layer having an uneven shape, and
A second step of applying an adhesive on the surface layer so as to fill the uneven concave portion of the surface layer and laminating the adhesive layer.
The third step of laminating the release film layer on the adhesive layer, and
A method of manufacturing a decorative sheet.
Item 26. Item 2. The method for manufacturing a decorative sheet according to Item 25, wherein the first step comprises the following steps.
The process of laminating the pattern layer and the primer layer on the base material layer in this order,
A step of embossing from the top of the primer layer to form an uneven shape on the surface of the primer layer,
A step of applying a curable resin composition on top of the primer layer, curing it, and laminating a surface layer having an uneven shape.
Item 27. Item 2. The method for manufacturing a decorative sheet according to Item 25, wherein the first step comprises the following steps.
The process of preparing a surface layer made of a resin film and
A step of embossing from above the surface layer to form an uneven shape on the surface of the surface layer.
Item 28. Item 2. The method for manufacturing a decorative sheet according to Item 25, wherein the first step comprises the following steps.
A step of laminating a pattern layer and a primer layer on the base material layer in this order,
A step of laminating a resin film on the primer layer and laminating a surface layer,
A step of embossing from above the surface layer to form an uneven shape on the surface of the surface layer.
Item 29. At least, a molding resin layer, a surface layer having an uneven shape, and a peelable uneven protective layer are laminated in this order.
The concavo-convex protective layer is a decorative resin molded product with a concavo-convex protective layer, which includes an adhesive layer that fills the concavo-convex recesses of the surface layer and a release film layer in this order from the surface layer side.
Item 30. Item 29. A method for producing a decorative resin molded product, comprising a step of peeling the uneven protective layer from the decorative resin molded product with the uneven protective layer according to Item 29.
Item 31. Item 8. A method for producing a decorative resin molded product with a concavo-convex protective layer, comprising a step of forming a molding resin layer by injecting a resin onto the surface layer side of the decorative sheet according to any one of Items 18 to 24.

According to the present invention, it is possible to provide a decorative sheet capable of imparting an excellent design feeling and a feeling of touch to a resin molded product due to its uneven shape. Further, according to the present invention, it is also possible to provide a decorative resin molded product using the decorative sheet and a method for producing the same.

It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded article with the thermoplastic resin film layer of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded article with the thermoplastic resin film layer of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded article of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded article of the first invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the second invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the second invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative sheet of the second invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded article with the concavo-convex protective layer of the second invention. It is a schematic diagram of the cross-sectional structure of one form of the decorative resin molded article of the second invention.

1. 1. Decorative sheet The decorative sheet of the first invention is formed by at least a base material layer, a cured product of a curable resin composition, a surface layer having an uneven shape, and a removable thermoplastic resin film layer. It is characterized in that it is laminated in this order.

Further, the decorative sheet of the second invention is formed by laminating at least a surface layer having a concavo-convex shape and a peelable concavo-convex protective layer, and the concavo-convex protective layer is formed in order from the surface layer side. It is characterized in that it is provided with an adhesive layer that fills the concave-convex-shaped recesses and a release film layer.

In the present specification, unless otherwise specified, "(meth) acrylic acid" means "acrylic acid or methacrylic acid", and other similar notations have the same meaning. Further, the decorative sheet of the present invention does not have to have a pattern layer or the like, and may be transparent, for example.

Hereinafter, the decorative sheet of the present invention will be described in detail. In the following description, the contents that are not common to the first invention and the second invention are specified, and unless otherwise specified, they are common, and therefore the description is omitted in the second invention. For example, in the first invention and the second invention, each of the base material layer 1, the ionizing radiation curable resin, the mold release layer 32, the primer layer 4, the pattern layer 5, the concealing layer, the transparent resin layer 6, and the back surface adhesive layer. The configuration is common. Further, the method for manufacturing the decorative resin molded product with the uneven protective layer is also common except that the decorative sheet of the second invention is used instead of the decorative sheet of the first invention.

Laminated structure of decorative sheet The decorative sheet of the first invention is formed of at least a base material layer 1, a cured product of a curable resin composition, a surface layer 2 having an uneven shape, and a removable thermoplastic resin. The film layer 30 has a laminated structure in which the film layers 30 are laminated in this order. The surface layer 2 may be composed of a plurality of layers.

In the first invention, the surface layer 2 and the thermoplastic resin film layer 30 may be directly laminated, or another layer may be laminated between these layers. When the thermoplastic resin film layer 30 is directly laminated, the thermoplastic resin film layer 30 becomes the unevenness protective layer 3 that protects the uneven shape of the surface layer 2. Further, when another layer is laminated between the surface layer 2 and the thermoplastic resin film layer 30, the other layer and the thermoplastic resin film layer 30 can function as the unevenness protective layer 3. Examples of the other layer include an adhesive layer 31 and a release layer 32.

In the first invention, when other layers are laminated, a laminate in which the adhesive layer 31 / thermoplastic resin film layer 30 is laminated in order from the surface layer 2 side; the release layer 32 / the thermoplastic resin. A laminate in which the film layer 30 is laminated; a laminate in which the release layer 32 / the adhesive layer 31 / the thermoplastic resin film layer 30 are laminated can each function as the unevenness protective layer 3.

In the first invention, the release layer 32 fills the concave-convex concave portion of the surface layer 2. When the adhesive layer 31 is formed of an adhesive, the adhesive layer 31 fills the concave-convex concave portion of the surface layer 2. Further, when the release layer 32 and the adhesive layer 31 formed by the adhesive are laminated, in the decorative sheet of the first invention, the release layer 32 and the adhesive layer 31 are The concave-convex concave portion of the surface layer 2 is filled. As described later, the adhesive layer 31 means an adhesive layer or an adhesive layer, and is formed of an adhesive or an adhesive.

In the decorative sheet of the first invention, a primer layer 4 may be provided between the base material layer 1 and the surface layer 2 as needed for the purpose of enhancing the adhesiveness between the layers. When the surface layer 2 is composed of a plurality of layers, for example, the plurality of surface layers 2 may be laminated via the primer layer 4.

Further, in the first invention, a pattern layer is required between the base material layer 1 and the surface layer 2 and on the side of the base material layer 1 opposite to the surface layer 2 for the purpose of imparting decorativeness. 5 may be provided. When the primer layer 4 is provided, the pattern layer 5 may be provided between the base material layer 1 and the primer layer 4. The pattern layer 5 may be provided in a plurality of layers.

Further, in the first invention, a concealing layer (not shown) is provided between the base material layer 1 and the surface layer 2 as necessary for the purpose of suppressing color change and variation of the base material layer 1. It may have been. When the primer layer 4 is provided, the concealing layer may be provided between the base material layer 1 and the primer layer 4, and when the pattern layer 5 is provided, the concealing layer is the base material layer. It may be provided between 1 and the pattern layer 5.

Further, in the first invention, a transparent resin layer 6 may be provided between the base material layer 1 and the surface layer 2 as needed for the purpose of improving scratch resistance. When the primer layer 4 is provided, the transparent resin layer 6 may be provided between the pattern layer 5 and the primer layer 4.

Further, in the decorative sheet of the first invention, for the purpose of improving the adhesion with the molding resin when molding the decorative resin molded product, the back surface of the base material layer 1 (on the side opposite to the surface layer 2). A back surface adhesive layer (not shown) may be provided on the surface), if necessary.

In the decorative sheet of the first invention, for the purpose of improving scratch resistance, weather resistance, etc. of the decorative resin molded product, directly under the surface layer 2 (on the side opposite to the thermoplastic resin film layer 30). , The resin layer 7 may be provided. When the resin layer 7 is provided, it is directly below the resin layer 7 (on the opposite side of the surface layer 2), if necessary, for the purpose of improving the adhesion between the resin layer 7 and the layer located below the resin layer 7. , An adhesive layer (not shown) may be provided.

As an example of the laminated structure of the decorative sheet of the first invention, the laminated structure in which the base material layer 1 / surface layer 2 / thermoplastic resin film layer 30 are laminated in order; the base material layer 1 / surface layer 2 / adhesive adhesion Laminated structure in which the layer 31 / thermoplastic resin film layer 30 is laminated in order; the laminated structure in which the base material layer 1 / surface layer 2 / release layer 32 / adhesive layer 31 / thermoplastic resin film layer 30 are laminated in order. Laminated structure in which the base material layer 1 / pattern layer 5 / surface layer 2 / thermoplastic resin film layer 30 are laminated in this order; base material layer 1 / pattern layer 5 / surface layer 2 / adhesive layer 31 / thermoplastic resin Laminated structure in which the film layers 30 are laminated in order; Laminated structure in which the base material layer 1 / pattern layer 5 / surface layer 2 / release layer 32 / adhesive layer 31 / thermoplastic resin film layer 30 are laminated in order; Laminated structure in which the material layer 1 / pattern layer 5 / primer layer 4 / surface layer 2 / thermoplastic resin film layer 30 are laminated in this order; base material layer 1 / pattern layer 5 / primer layer 4 / surface layer 2 / adhesive adhesion Laminated structure in which layer 31 / thermoplastic resin film layer 30 are laminated in order; base material layer 1 / pattern layer 5 / primer layer 4 / surface layer 2 / mold release layer 32 / adhesive layer 31 / thermoplastic resin film layer Laminated structure in which 30 are laminated in order; Laminated structure in which base material layer 1 / pattern layer 5 / transparent resin layer 6 / primer layer 4 / surface layer 2 / thermoplastic resin film layer 30 are laminated in order; base material layer 1 / Laminated structure in which the pattern layer 5 / transparent resin layer 6 / primer layer 4 / surface layer 2 / adhesive layer 31 / thermoplastic resin film layer 30 are laminated in this order; base material layer 1 / pattern layer 5 / transparent resin layer 6 / Primer layer 4 / Surface layer 2 / Release layer 32 / Adhesive layer 31 / Thermoplastic resin film layer 30 are laminated in this order; Base material layer 1 / Picture layer 5 / Transparent resin layer 6 / Adhesive Laminated structure in which the layer / resin layer 7 / surface layer 2 / release layer 32 / adhesive layer 31 / thermoplastic resin film layer 30 are laminated in this order; pattern layer 5 / base material layer 1 / pattern layer 5 / transparent resin Laminated structure in which layer 6 / primer layer 4 / surface layer 2 / release layer 32 / adhesive layer 31 / thermoplastic resin film layer 30 are laminated in this order; base material layer 1 / pattern layer 5 / transparent resin layer 6 / Laminated structure in which surface layer 2 / primer layer 4 / surface layer 2 / release layer 32 / adhesive layer 31 / thermoplastic resin film layer 30 are laminated in this order; base material layer 1 / pattern layer 5 / transparent resin layer 6 / Primer layer 4 / Resin layer 7 / Surface layer 2 / Release layer 32 / Adhesive layer 31 / Thermoplastic resin film layer 30 are laminated in this order.

1 to 3 show a cross-sectional view of the decorative sheet in which the base material layer 1 / surface layer 2 / thermoplastic resin film layer 30 are laminated in this order as one aspect of the laminated structure of the decorative sheet of the first invention. show. FIG. 4 shows, as one aspect of the laminated structure of the decorative sheet of the first invention, the base material layer 1 / the pattern layer 5 / the transparent resin layer 6 / the primer layer 4 / the surface layer 2 / the release layer 32 / adhesive adhesion. The cross-sectional view of the decorative sheet in which a layer 31 / a thermoplastic resin film layer 30 is laminated in order is shown. FIG. 5 shows, as one aspect of the laminated structure of the decorative sheet of the first invention, the base material layer 1 / the pattern layer 5 / the transparent resin layer 6 / the primer layer 4 / the resin layer 7 / the surface layer 2 / the release layer 32. The cross-sectional view of the decorative sheet in which the adhesive layer 31 / the thermoplastic resin film layer 30 are laminated in order is shown. FIG. 6 shows, as one aspect of the laminated structure of the decorative sheet of the first invention, the pattern layer 5 / base layer 1 / pattern layer 5 / transparent resin layer 6 / primer layer 4 / surface layer 2 / release layer 32. A cross-sectional view of a decorative sheet in which the adhesive layer 31 / thermoplastic resin film layer 30 is laminated in this order is shown. In FIG. 7, as one aspect of the laminated structure of the decorative sheet of the first invention, the base material layer 1 / the pattern layer 5 / the transparent resin layer 6 / the surface layer 2 / the primer layer 4 / the surface layer 2 / the release layer 32. The cross-sectional view of the decorative sheet in which the adhesive layer 31 / the thermoplastic resin film layer 30 is laminated in order is shown.

The decorative sheet of the second invention has at least a laminated structure in which a surface layer 2 having a concavo-convex shape and a peelable concavo-convex protective layer 3 are laminated.

The concavo-convex protective layer 3 includes an adhesive layer 34 that fills the concavo-convex concave recesses of the surface layer 2 and a release film layer 33 in this order from the surface layer 2 side. For the purpose of improving the peelability between the surface layer 2 and the unevenness protective layer 3, in the unevenness protective layer 3, the release layer 32, the adhesive layer 34, and the release film layer 33 are sequentially arranged from the surface layer 2 side. May be laminated. When the concave-convex protective layer 3 has the release layer 32, in the decorative sheet of the second invention, the release layer 32 and the adhesive layer 34 fill the concave-convex-shaped recesses of the surface layer 2.

In the decorative sheet of the second invention, the base material layer 1 may be provided on the side of the surface layer 2 opposite to the unevenness protective layer 3 as a support for the decorative sheet.

In the decorative sheet of the second invention, a primer layer 4 may be provided on the side of the surface layer 2 opposite to the unevenness protective layer 3 for the purpose of enhancing the adhesiveness between the layers, if necessary.

Further, on the side of the surface layer 2 opposite to the unevenness protective layer 3, a pattern layer 5 may be provided, if necessary, for the purpose of imparting decorativeness. When the base material layer 1 and the primer layer 4 are provided, the pattern layer 5 may be provided between the base material layer 1 and the primer layer 4.

Further, when the base material layer 1 is provided, a concealing layer (not shown) is provided between the base material layer 1 and the surface layer 2 as necessary for the purpose of suppressing color change and variation of the base material layer 1. May be provided. When the primer layer 4 is provided, the concealing layer may be provided between the base material layer 1 and the primer layer 4, and when the pattern layer 5 is provided, the concealing layer is the base material layer. It may be provided between 1 and the pattern layer 5.

Further, a transparent resin layer 6 may be provided on the side of the surface layer 2 opposite to the unevenness protective layer 3 for the purpose of improving scratch resistance, if necessary. When the primer layer 4 is provided, the transparent resin layer 6 may be provided between the pattern layer 5 and the primer layer 4.

Further, in the decorative sheet of the second invention, on the surface of the surface layer 2 opposite to the uneven protective layer 3 for the purpose of improving the adhesion with the molding resin when molding the decorative resin molded product. May be provided with a back surface adhesive layer (not shown), if necessary.

As an example of the laminated structure of the decorative sheet of the second invention, the laminated structure in which the surface layer 2 / the unevenness protective layer 3 (adhesive layer 34 / release film layer 33) is laminated in order; the base material layer 1 / surface layer 2 / Laminated structure in which the unevenness protective layer 3 (adhesive layer 34 / release film layer 33) is laminated in order; the base material layer 1 / pattern layer 5 / surface layer 2 / unevenness protective layer 3 (adhesive layer 34 / release film layer 33) Laminated structure in which the base material layer 1 / picture layer 5 / primer layer 4 / surface layer 2 / unevenness protective layer 3 (adhesive layer 34 / release film layer 33) are laminated in order; base material layer 1 / Pattern layer 5 / Primer layer 4 / Surface layer 2 / Concavo-convex protection layer 3 (Release layer 32 / Adhesive layer 34 / Release film layer 33) are laminated in this order; Base material layer 1 / Design layer 5 / Transparent Examples thereof include a laminated structure in which a resin layer 6 / a primer layer 4 / a surface layer 2 / a concave-convex protective layer 3 (a release layer 32 / an adhesive layer 34 / a release film layer 33) are laminated in this order. In FIGS. 12 and 13, as one aspect of the laminated structure of the decorative sheet of the second invention, the base material layer 1 / surface layer 2 / unevenness protective layer 3 (adhesive layer 34 / release film layer 33) are laminated in this order. The cross-sectional view of the decorative sheet is shown. In FIG. 12, as one aspect of the laminated structure of the decorative sheet of the second invention, the base material layer 1 / the pattern layer 5 / the transparent resin layer 6 / the primer layer 4 / the surface layer 2 / the unevenness protective layer 3 (release layer). A cross-sectional view of a decorative sheet in which a laminated structure in which 32 / adhesive layer 33 / release film layer 33) is laminated in order is shown.

Composition of each layer of decorative sheet [Base material layer 1]
The base material layer 1 is a resin sheet (resin film) that serves as a support in the decorative sheet of the present invention (first and second inventions). The resin component used for the base material layer 1 is not particularly limited and may be appropriately selected depending on the three-dimensional moldability, compatibility with the molding resin, etc., but a resin film made of a thermoplastic resin is preferable. Can be mentioned. Specific examples of the thermoplastic resin include acrylonitrile-butadiene-styrene resin (hereinafter sometimes referred to as "ABS resin") and acrylonitrile-styrene-acrylic acid ester resin (hereinafter referred to as "ASA resin"). ), Acrylic resin, polyolefin resin such as polypropylene, polyethylene, polycarbonate resin, vinyl chloride resin, polyethylene terephthalate (PET) and the like. Among these, ABS resin and acrylic resin are preferable from the viewpoint of three-dimensional moldability. Further, the base material layer 1 may be formed of a single-layer sheet of these resins, or may be formed of a multi-layer sheet of the same or different resins.

The flexural modulus of the base material layer 1 is not particularly limited. For example, when the decorative sheet of the present invention is integrated with a molding resin by an insert molding method, the flexural modulus of the base material layer 1 of the decorative sheet of the present invention at 25 ° C. is preferably 500 to 4,000 MPa. 750 to 3,000 MPa can be mentioned. Here, the flexural modulus at 25 ° C. is a value measured in accordance with JIS K7171. When the flexural modulus at 25 ° C. is 500 MPa or more, the decorative sheet has sufficient rigidity, and the surface characteristics and moldability are further improved even when subjected to the insert molding method. Further, when the flexural modulus at 25 ° C. is 3,000 MPa or less, sufficient tension can be applied in the case of roll-to-roll manufacturing, and slack is less likely to occur. The so-called pattern register becomes good.

The base material layer 1 is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides, if necessary, in order to improve the adhesion to the layer provided on the base material layer 1. You may. Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. Further, examples of the unevenness method performed as the surface treatment of the base material layer 1 include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of resin component constituting the base material layer 1, but from the viewpoint of effect and operability, a corona discharge treatment method is preferable.

Further, the base material layer 1 may be subjected to a treatment such as forming a known adhesive layer.

Further, the base material layer 1 may or may not be colored with a colorant. Further, the base material layer 1 may be in any of colorless transparent, colored transparent, and translucent modes. The colorant used for the base material layer 1 is not particularly limited, but preferably a colorant that does not discolor even under a temperature condition of 150 ° C. or higher, and specifically, an existing dry color, paste color, or masterbatch resin. Examples include compositions.

The thickness of the base material layer 1 is appropriately set depending on the intended use of the decorative sheet, the molding method for integrating with the molding resin, and the like, and is usually about 25 to 1000 μm and about 50 to 700 μm. More specifically, when the decorative sheet of the present invention is subjected to the insert molding method, the thickness of the base material layer 1 is usually about 50 to 1000 μm, preferably 100 to 700 μm, and more preferably 100 to 500 μm. Can be mentioned. When the decorative sheet of the present invention is subjected to the injection molding simultaneous decoration method, the thickness of the base material layer 1 is usually 25 to 200 μm, preferably 50 to 200 μm, and more preferably 70 to 200 μm. ..

[Surface layer 2]
In the first invention, the surface layer 2 has an uneven shape and is formed of a cured product of a curable resin composition (resin composition containing a curable resin). By forming the surface layer 2 having an uneven shape with a cured product of the curable resin composition in this way, the uneven shape is deformed when the thermoplastic resin film layer 30 described later is laminated on the surface layer 2. It can be suppressed from disappearing or disappearing. Therefore, by using the decorative sheet of the first invention, when a conventional decorative sheet in which a removable thermoplastic resin film layer is laminated on a thermoplastic base sheet as a surface layer having an uneven shape is used. It is possible to obtain a decorative resin molded product having an excellent design feeling and a feeling of touch. The surface layer 2 may be composed of a plurality of layers. When the surface layer 2 is composed of a plurality of layers, for example, as shown in FIG. 7, the plurality of surface layers 2 can be laminated via the primer layer 4. By forming the surface layer with a plurality of layers, it is possible to impart different functions to each surface layer.

Further, in the second invention, the surface layer 2 has an uneven shape, and is preferably formed of a cured product or a resin film of a curable resin composition.

<Concave and convex shape>
In the first and second inventions, the uneven shape formed on the surface layer 2 is not particularly limited, and may be appropriately set according to the design feeling, the feel, and the like to be imparted. Examples of the uneven shape include a hairline pattern, a wood grain pattern, a geometric pattern (dots, stripes, carbon) and the like.

Further, the height of the convex portion, the width of the convex portion, the pitch between the adjacent convex portions, the width of the concave portion, etc. in the concave-convex shape formed on the surface layer 2 are appropriately determined according to the design feeling to be given, the feel, and the like. Just set it.

For example, the average roughness (Ra) of the center line of the surface layer 2 is usually 1.0 to 20 μm, preferably 1.0 to 10 μm, more preferably 1.0 to 10 μm, from the viewpoint of imparting an excellent design feeling and feel due to the uneven shape. Examples include 1.5 to 5 μm. If the average roughness of the center line of the surface layer 2 is 20 μm or less, the decorative sheet may be damaged or torn during transportation, or the roll may be broken due to excessive unevenness when the decorative sheet is rolled and stored. Etc. do not occur and are suitable.

From the same viewpoint, the maximum height (Rmax) is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, and more preferably 1.0 to 60 μm. From the same viewpoint, the ten-point average height (Rz) is usually 1.0 to 100 μm, preferably 1.0 to 80 μm, and more preferably 1.0 to 60 μm. The center line average roughness (Ra), maximum height (Rmax), and ten-point average height (Rz) are values measured using a surface roughness / contour shape measuring machine, respectively.

Further, in the first invention, the concave-convex shape formed by the surface layer 2 may have the bottom of the recess formed by the surface layer 2 as shown in FIG. 1, and FIGS. 2 and 3 show. As shown in the embodiment, the lower layer of the surface layer 2 may be exposed at the bottom of the recess, and the surface layer 2 may be partially provided to form a convex portion. The former is preferable from the viewpoint of protecting the surface of the decorative resin molded product. 1 and 2 show, for example, a concave-convex shape formed by a method of embossing, which will be described later, and FIG. It shows the uneven shape formed by the method of applying and curing only the upper layer). That is, in FIG. 3, the uneven shape of the surface layer 2 is formed by a partially provided convex portion and a concave portion in which the lower layer of the surface layer is exposed between the convex portions. 1 to 3 show a laminated structure in which the base material layer 1, the surface layer 2, and the peelable thermoplastic resin film layer 30 are laminated in this order for convenience.

From the viewpoint of providing an excellent design feeling and a feeling of touch, it is preferable that the decorative sheet is provided with the pattern layer 5, and that the concave-convex concave portion formed by the surface layer 2 reaches the pattern layer 5. ..

On the other hand, in the second invention, the concave-convex shape formed by the surface layer 2 may have the bottom of the recess formed by the surface layer 2 as in the embodiment shown in FIG. 12, or the embodiment shown in FIG. As described above, the lower layer of the surface layer 2 may be exposed at the bottom of the recess, and a plurality of convex portions of the surface layer 2 may be partially provided. The former is preferable from the viewpoint of protecting the surface of the decorative resin molded product. Note that FIGS. 12 and 13 show a laminated structure in which the base material layer 1, the surface layer 2, and the unevenness protective layer 3 are laminated in this order for convenience.

In the decorative sheets of the first and second inventions, the uneven shape may be formed in at least a part of the decorative sheet in order to give the decorative sheet a high texture due to the uneven shape. That is, in the decorative sheet of the present invention, the uneven shape satisfying the above relationship may be formed in a part of the region or the entire region.

<Composition>
In the cured product of the curable resin composition forming the surface layer 2 of the first invention, examples of the curable resin include thermosetting resins and ionizing radiation curable resins, and ionizing radiation curable resins are preferable. A surface layer having an uneven shape is formed of a cured product of a resin composition containing an ionizing radiation curable resin, and the surface layer is covered with a thermoplastic resin film layer described later, which is generated during vacuum molding or injection molding. It is possible to suppress deformation and disappearance of the uneven shape, and to give a particularly excellent design feeling and touch feeling to the decorative resin molded product.

On the other hand, examples of the resin film forming the surface layer 2 of the second invention include a thermoplastic resin film. Examples of the thermoplastic resin include polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), and acrylic resins, and acrylic resins are preferable. When the surface layer 2 is formed of a resin film, the surface layer 2 is usually self-supporting and can serve as a support. Therefore, in this case, the decorative sheet of the first invention does not have to have the base material layer 1.

In the first and second inventions, examples of the thermosetting resin include urethane resin and epoxy resin. One type of thermosetting resin may be used alone, or two or more types may be used in combination. When a thermosetting resin is used, the surface layer 2 can be formed by laminating the thermosetting resin before curing and heat-curing it. The ionizing radiation curable resin is as follows.

(Ionizing radiation curable resin)
In the first and second inventions, the ionizing radiation curable resin used for forming the surface layer 2 refers to a resin that is crosslinked and cured by irradiation with ionizing radiation. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually ultraviolet rays (UV) or electron beams (EB) are used, but other , X-rays, γ-rays and other electromagnetic waves, α-rays, ion-rays and other charged particle rays are also included. Among the ionizing radiation curable resins, the electron beam curable resin can be made solvent-free, does not require a photopolymerization initiator, and has stable curing properties, and is therefore preferably used in the formation of a surface layer. Will be done.

Specific examples of the ionizing thermosetting resin include those obtained by appropriately mixing a prepolymer, an oligomer, and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule.

As the above-mentioned oligomer used as an ionizing radiation curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, two or more polymerizable unsaturated bonds (2) in the molecule. A polyfunctional (meth) acrylate oligomer having (more than functional) is preferable. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, silicone-modified urethane (meth) acrylate, oligomers having a cationically polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic Group vinyl ether, etc.) and the like. Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain, and for example, a polycarbonate polyol (meth) is used. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyisocyanate compound, and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with the oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate in which this epoxy (meth) acrylate is partially modified with a dibasic carboxylic acid anhydride can also be used. The polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or to a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. The silicone-modified urethane (meth) acrylate can be obtained, for example, by reacting a urethane prepolymer having an isocyanate group with a silicone compound having a silanol group together with hydroxy (meth) acrylate. These oligomers may be used alone or in combination of two or more.

Further, as the above-mentioned monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer may be any (meth) acrylate monomer having two or more polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di. (Meta) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (Meta) Acrylate, Ethylene Oxide Modified Di (Meta) Acrylate, Allylated Cyclohexyl Di (Meta) Acrylate, Isocyanurate Di (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Ethylene Oxide Modified Trimethylol Propantri (Meta) Acrylate, dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propantri (meth) acrylate, tris (acryloxyethyl) isocia Examples thereof include nurate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. These monomers may be used alone or in combination of two or more.

Among these ionizing radiation curable resins, an oligomer having a polymerizable unsaturated bond or an epoxy group in the molecule is preferable from the viewpoint of imparting an even more excellent design feeling and touch feeling to the decorative resin molded product. , More preferably polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, and particularly preferably polycarbonate (meth) acrylate.

Among these ionizing radiation curable resins, (1) polycarbonate (meth) acrylate and (2) other polyfunctionality (2) are preferable from the viewpoint of imparting a remarkably excellent design feeling and touch feeling. Combinations of meta) acrylates (polyfunctional (meth) acrylate oligomers or monomers); more preferred include combinations of (1) polycarbonate (meth) acrylates and (2) polyfunctional urethane (meth) acrylates.

When the ionizing radiation curable resin of (1) and the ionizing radiation curable resin of (2) are used in combination, the ratios thereof may be set in consideration of their molecular weight, the number of functional groups, and the like. For example, the mass ratio of the ionizing radiation curable resin of (1) to the ionizing radiation curable resin of (2) (ionizing radiation curable resin of (1): ionizing radiation curable resin of (2)). However, preferably about 50:50 to 99: 1, more preferably about 80:20 to 99: 1, and particularly preferably about 85: 15 to 99: 1.

Hereinafter, the polycarbonate (meth) acrylate and the polyfunctional urethane (meth) acrylate preferably used as the ionizing radiation curable resin for forming the surface layer 2 will be described in detail.

Polycarbonate (meth) acrylate The polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and has (meth) acrylate in the terminal or side chain, and has, for example, a polycarbonate skeleton. It may be urethane (meth) acrylate or the like. Further, from the viewpoint of improving cross-linking and curing of the (meth) acrylate, the number of functional groups per molecule is preferably 2 to 6. The polycarbonate (meth) acrylate is preferably a polyfunctional polycarbonate (meth) acrylate having two or more (meth) acrylates at the ends or side chains. One type of polycarbonate (meth) acrylate may be used alone, or two or more types may be used in combination.

The polycarbonate (meth) acrylate is obtained, for example, by converting some or all of the hydroxyl groups of the polycarbonate polyol into (meth) acrylate (acrylic acid ester or methacrylic acid ester). This esterification reaction can be carried out by a usual esterification reaction. For example, 1) a method of condensing a polycarbonate polyol and an acrylic acid halide or a methacrylate halide in the presence of a base, and 2) a method of condensing a polycarbonate polyol and an acrylic acid anhydride or a methacrylate anhydride in the presence of a catalyst. Alternatively, 3) a method of condensing a polycarbonate polyol and acrylic acid or methacrylic acid in the presence of an acid catalyst can be mentioned.

The polycarbonate polyol is a polymer having a carbonate bond in the polymer main chain and having two or more, preferably 2 to 50, more preferably 3 to 50 hydroxyl groups in the terminal or side chain. A typical method for producing the polycarbonate polyol is a method by polycondensation reaction with a diol compound (A), a trihydric or higher polyhydric alcohol (B), and a compound (C) as a carbonyl component.

The diol compound (A) used as a raw material for the polycarbonate polyol is represented by ^{the general formula HO-R 1-OH.} Here, R ¹ is a divalent hydrocarbon group having 2 to 20 carbon atoms, and may contain an ether bond in the group. For example, a linear or branched alkylene group, a cyclohexylene group, or a phenylene group.

Specific examples of the diol compound include ethylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, neopentyl glycol, 1,3-propanediol, and 1,4-butanediol. 1,5-Pentanediol, 3-Methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-Hydroxyethoxy) benzene, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. These diols may be used alone or in combination of two or more.

Examples of trihydric or higher polyhydric alcohols (B) used as raw materials for polycarbonate polyols include alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, glycerin, and sorbitol. Can be mentioned. Further, the trihydric or higher polyhydric alcohol may be an alcohol having a hydroxyl group obtained by adding 1 to 5 equivalents of ethylene oxide, propylene oxide, or other alkylene oxide to the hydroxyl group of the polyhydric alcohol. good. These polyhydric alcohols may be used alone or in combination of two or more.

The compound (C) as a carbonyl component used as a raw material for the polycarbonate polyol is a compound selected from a carbonic acid diester, phosgene, or an equivalent thereof. Specific examples of the compound include carbonate diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate; phosgene; formic acid halide such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. Esters and the like can be mentioned. These compounds may be used alone or in combination of two or more.

The polycarbonate polyol is synthesized by polycondensing the diol compound (A), the trihydric or higher polyhydric alcohol (B), and the compound (C) as a carbonyl component under general conditions. The charged molar ratio of the diol compound (A) and the polyhydric alcohol (B) may be set in the range of, for example, 50:50 to 99: 1. The molar ratio of the compound (C) to be the carbonyl component to the diol compound (A) and the polyhydric alcohol (B) is, for example, 0.2 to 2 with respect to the hydroxyl groups of the diol compound and the polyhydric alcohol. It may be set in the equivalent range.

The equivalent number (eq. / Mol) of the hydroxyl groups present in the polycarbonate polyol after the polycondensation reaction at the above-mentioned charging ratio is, for example, 3 or more, preferably 3 to 50, more preferably 3 to 50 on average in one molecule. 3 to 20 can be mentioned. When such an equal amount is satisfied, a required amount of (meth) acrylate groups is formed by the esterification reaction described later, and appropriate flexibility is imparted to the polycarbonate (meth) acrylate resin. The terminal functional group of this polycarbonate polyol is usually an OH group, but a part thereof may be a carbonate group.

The method for producing a polycarbonate polyol described above is described in, for example, Japanese Patent Application Laid-Open No. 64-1726. Further, as described in Japanese Patent Application Laid-Open No. 3-181517, this polycarbonate polyol can also be produced by a transesterification reaction between a polycarbonate diol and a polyhydric alcohol having a valence of 3 or more.

The molecular weight of the polycarbonate (meth) acrylate is not particularly limited, and examples thereof include a weight average molecular weight of 500 or more, preferably 1,000 or more, and more preferably 2,000 or more. The upper limit of the weight average molecular weight of the polycarbonate (meth) acrylate is not particularly limited, but from the viewpoint of controlling the viscosity so as not to become too high, for example, 100,000 or less, preferably 50,000 or less can be mentioned. The weight average molecular weight of the polycarbonate (meth) acrylate is preferably more than 2,000 and less than 50,000, more preferably 5,000 to 20,000, from the viewpoint of further improving moldability.

The weight average molecular weight of the polycarbonate (meth) acrylate in the present specification is a value measured by a gel permeation chromatography method using polystyrene as a standard substance.

<Polyfunctional urethane (meth) acrylate>
The polyfunctional urethane (meth) acrylate is not particularly limited as long as it has a urethane bond in the polymer main chain and has a (meth) acrylate in the terminal or side chain. Such urethane (meth) acrylates can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate with (meth) acrylic acid. Further, from the viewpoint of improving cross-linking and curing of urethane (meth) acrylate, the number of functional groups per molecule is preferably 2 to 12. The ionizing radiation curable resin composition used for forming the surface layer 2 may further contain urethane (meth) acrylate in addition to the above-mentioned polycarbonate (meth) acrylate. One type of urethane (meth) acrylate may be used alone, or two or more types may be used in combination.

The molecular weight of the urethane (meth) acrylate is not particularly limited, and examples thereof include a weight average molecular weight of 2,000 or more, preferably 5,000 or more. The upper limit of the weight average molecular weight of the urethane (meth) acrylate is not particularly limited, but from the viewpoint of controlling the viscosity so as not to become too high, for example, 30,000 or less, preferably 10,000 or less can be mentioned.

The weight average molecular weight of urethane (meth) acrylate in the present specification is a value measured by a gel permeation chromatography method using polystyrene as a standard substance.

<Silicone-based ionizing radiation curable resin>
By including a silicone-based ionizing radiation-curable resin as the ionizing radiation-curable resin forming the surface layer 2, the thermoplastic resin film layer 30 can be easily peeled off from the decorative resin molded product, and the design feeling is excellent. And a feeling of touch can be imparted.

The silicone-based ionizing radiation curable resin is not particularly limited, but preferably includes acrylic silicone (meth) acrylate, silicone acrylate, and silicone-modified urethane (meth) acrylate, and particularly preferably acrylic silicone (meth) acrylate. .. In the present invention, "acrylic silicone (meth) acrylate" means "a part of the structure of the acrylic resin is replaced with a siloxane bond (Si—O) in one molecule, and the acrylic resin is used as a functional group. It means that it has two or more (meth) acryloyloxy groups at the end of the side chain and / or the main chain of the above. Further, the "silicone (meth) acrylate" means "a modified silicone oil in which (meth) acryloyl groups are introduced into the side chains and both ends of the silicone oil having polysiloxane as the main chain". Hereinafter, acrylic silicone (meth) acrylate, silicone (meth) acrylate, and silicone-modified urethane (meth) acrylate, which are preferable as silicone-based ionizing radiation curable resins, will be described in detail.

(Acrylic silicone (meta) acrylate)
The acrylic silicone (meth) acrylate is not particularly limited, and a part of the structure of the acrylic resin is replaced with a siloxane bond (Si—O) in one molecule, and the side chain of the acrylic resin and / or as a functional group. Alternatively, it may have two or more (meth) acryloyloxy groups (acryloyloxy groups or metaacryloyloxy groups) at the end of the main chain. As an example of this acrylic silicone (meth) acrylate, for example, a structure of an acrylic resin having a siloxane bond in the side chain as disclosed in JP-A-2007-0705444 is preferably mentioned.

The acrylic silicone (meth) acrylate used in the present invention can be synthesized, for example, by radically copolymerizing a silicone macromonomer with a (meth) acrylate monomer in the presence of a radical polymerization initiator. Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and glycidyl (meth) acrylate. These (meth) acrylate monomers may be used alone or in combination of two.

The silicone macromonomer is synthesized, for example, by using n-butyllithium or lithium silanolate as a polymerization initiator, hexaalkylcyclotrisiloxane is subjected to living anionic polymerization, and further capped with a radically polymerizable unsaturated group-containing silane. The silicone macromonomer has the following formula (1);

で表される化合物が好適に用いられる。ここで、式（１）中、Ｒ¹は、炭素数１〜４のアルキル基を示し、メチル基又はｎ−ブチル基が好ましい。Ｒ²は、１価の有機基を示し、−ＣＨ＝ＣＨ₂、−Ｃ₆Ｈ₄−ＣＨ＝ＣＨ₂、−（ＣＨ₂）₃Ｏ（ＣＯ）ＣＨ＝ＣＨ₂又は−（ＣＨ₂）₃Ｏ（ＣＯ）Ｃ（ＣＨ₃）＝ＣＨ₂が好ましい。Ｒ³は、それぞれ同一であっても異なっていてもよく、炭素数１〜６の炭化水素基を示し、炭素数１〜４のアルキル基又はフェニル基が好ましく、メチル基がより好ましい。また、ｎの数値は特に制限されず、例えばシリコーンマクロモノマーの数平均分子量が１，０００〜３０，０００が好ましく、１，０００〜２０，０００がより好ましい。

The compound represented by is preferably used. Here, in the formula (1), R ¹ represents an alkyl group having 1 to 4 carbon atoms, and a methyl group or an n-butyl group is preferable. R ² represents a monovalent organic group, −CH = CH ₂ , −C ₆ H ₄ −CH = CH ₂ , − (CH ₂ ) ₃ O (CO) CH = CH ₂ or − (CH ₂ ) ₃ O (CO) C (CH ₃ ) = CH ₂ is preferable. R ³ may be the same or different, and represents a hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group or a phenyl group having 1 to 4 carbon atoms, and more preferably a methyl group. The value of n is not particularly limited, and for example, the number average molecular weight of the silicone macromonomer is preferably 1,000 to 30,000, more preferably 1,000 to 20,000.

The acrylic silicone (meth) acrylate obtained by using the above-mentioned raw materials has, for example, structural units represented by the following formulas (2), (3) and (4).

式（２）、（３）及び（４）中、Ｒ¹、Ｒ³は式（１）におけるものと同義であり、Ｒ⁴は水素原子又はメチル基を示し、Ｒ⁵は上記（メタ）アクリレートモノマー中のアルキル基又はグリシジル基あるいは上記（メタ）アクリレートモノマー中のアルキル基又はグリシジル基等の官能基を有していてもよいアルキル基を示し、Ｒ⁶は（メタ）アクリロイルオキシ基を有する有機基を示す。上述のアクリルシリコーン（メタ）アクリレートは、１種を単独で又は２種を組み合わせて用いられる。

In formulas (2), (3) and (4), R ¹ and R ³ are synonymous with those in formula (1), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ is the above (meth) acrylate. An alkyl group which may have a functional group such as an alkyl group or a glycidyl group in the monomer or an alkyl group or a glycidyl group in the (meth) acrylate monomer is shown, and R ⁶ is an organic having a (meth) acryloyloxy group. Indicates a group. The above-mentioned acrylic silicone (meth) acrylate may be used alone or in combination of two.

The molecular weight of the acrylic silicone (meth) acrylate is preferably 1,000 or more, and more preferably 2,000 or more, based on the weight average molecular weight measured by GPC analysis and converted into standard polystyrene. .. The upper limit of the weight average molecular weight of the acrylic silicone (meth) acrylate is not particularly limited, but is preferably 150,000 or less, more preferably 100,000 or less, from the viewpoint of controlling the viscosity so as not to become too high. From the viewpoint of improving the three-dimensional moldability, chemical resistance and scratch resistance, it is particularly preferably 2,000 to 100,000.

The average molecular weight between the cross-linking points of the acrylic silicone (meth) acrylate is preferably 100 to 2,500. When the average molecular weight between the cross-linking points is 100 or more, it is preferable from the viewpoint of three-dimensional moldability, and when it is 2,500 or less, it is preferable from the viewpoint of chemical resistance and scratch resistance. From the same viewpoint, the average molecular weight between the cross-linking points of the acrylic silicone (meth) acrylate is more preferably 100 to 1,500, still more preferably 100 to 1,000.

(Silicone (meth) acrylate)
The silicone (meth) acrylate is not particularly limited as long as it is a modified silicone oil in which (meth) acryloyl groups are introduced into the side chains of the silicone oil having a polysiloxane as the main chain or both ends, and monofunctional or bifunctional silicone. (Meta) acrylate and polyfunctional (trifunctional or higher) silicone (meth) acrylate can be used.

As the monofunctional or bifunctional silicone (meth) acrylate, conventionally known ones can be used, and the organic group is a (meth) acrylic group, and the modified silicone oil having one or two organic groups is particularly limited. Not done. The structure of the modified silicone oil is roughly classified into a side chain type, a double-ended type, a single-ended type, and a double-ended side chain type depending on the bonding position of the organic group to be substituted. , There are no particular restrictions. As such a silicone (meth) acrylate, the weight average molecular weight is preferably 1000 to 6000, more preferably 3000 to 6000, and the functional group equivalent (weight average molecular weight / number of functional groups) is preferably 500 to 3000, more preferably 1500 to 1500. Those having 3000 conditions are used.

Further, as the polyfunctional (trifunctional or higher) silicone (meth) acrylate used for the silicone (meth) acrylate, conventionally known ones can be used, and the organic group is a (meth) acrylic group, and a plurality of the organic groups are preferable. Is not particularly limited as long as it is a modified silicone oil having 4 or more, further 4 to 6. The structure of the modified silicone oil is roughly classified into a side chain type, a double-ended type, a single-ended type, and a double-ended side chain type depending on the bonding position of the organic group to be substituted. , There are no particular restrictions. The silicone (meth) acrylate preferably has a weight average molecular weight of 3,000 to 100,000, more preferably 1,000 to 30,000, and a functional group equivalent (weight average molecular weight / number of functional groups) of preferably 750 to 25,000, more preferably 3,000 to 3,000. Those having 6000 conditions are used.

The weight average molecular weight of the silicone (meth) acrylate in the present specification is a value measured by a gel permeation chromatography method using polystyrene as a standard substance.

(Silicone-modified urethane (meth) acrylate)
The silicone-modified urethane (meth) acrylate is not particularly limited, and examples thereof include compounds in which a part of the side chain of the urethane (meth) acrylate is modified with silicone. The silicone-modified urethane (meth) acrylate can be obtained, for example, by reacting a urethane prepolymer having an isocyanate group with a silicone compound having a silanol group together with hydroxy (meth) acrylate.

Regarding the number of functional groups and the molecular weight of the silicone-modified urethane (meth) acrylate, for example, the number of functional groups per molecule is 1 to 10, preferably 2 to 8, more preferably 3 to 6, and the weight average molecular weight is 1000 to. Examples thereof include 50,000, preferably 3000 to 30000, and more preferably 5000 to 10000.

The proportion of the silicone-based ionizing radiation curable resin in the ionizing radiation curable resin forming the surface layer 2 is preferably about 1 to 10% by mass, more preferably about 1 to 5% by mass, and further preferably about 3 to 3. About 5% by mass is mentioned.

<Other additives>
Further, various additives can be added to the curable resin composition used for forming the surface layer 2 according to the desired physical properties to be provided in the surface layer 2. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. , Chixo property imparting agent, coupling agent, plasticizer, defoaming agent, filler, solvent, colorant, wax and the like. These additives can be appropriately selected and used from those commonly used. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used. By blending wax, scratch resistance and wear resistance can be improved. The wax preferably includes an olefin wax such as polyethylene wax (PE wax). When the wax is blended, the blending amount in the curable resin composition is preferably about 0.1 to 5% by mass, more preferably about 0.5 to 3% by mass.

<Thickness of surface layer 2>
The thickness of the surface layer 2 after curing is not particularly limited, and examples thereof include 0.01 to 200 μm, preferably 0.01 to 100 μm, and more preferably 0.01 to 80 μm. By satisfying the thickness in such a range, the uneven shape can be expressed more effectively, and an excellent design feeling and a feeling of touch can be provided. Further, from the viewpoint of improving not only the design and feel of the decorative sheet but also the moldability, the thickness is preferably less than 50 μm, more preferably 0.01 to 40 μm. It is preferably 0.01 to 30 μm, and particularly preferably 0.01 to 30 μm. As shown in FIGS. 1, 2 and 4, for example, when the uneven shape is formed by embossing, the uneven shape is effectively expressed, and a particularly excellent design feeling and feel are obtained. From the viewpoint of providing a feeling, the thickness of the surface layer 2 after curing is preferably 0.01 to 20 μm, more preferably 0.01 to 15 μm, and further preferably 0.01 to 12 μm. The thickness of the surface layer 2 means the thickness of the convex portion of the surface layer 2.

<Formation of surface layer 2>
In the first invention, the surface layer 2 may be formed on a predetermined layer so that the cured product of the curable resin composition has an uneven shape, and the specific method thereof is not particularly limited. No. Examples of the method of imparting an uneven shape to the surface layer 2 include a method of embossing, a method of applying a resin composition forming the surface layer 2 only to a portion where a convex portion is formed, and a method of curing the surface layer 2. .. For example, from the viewpoint of imparting a fine uneven shape, a method of embossing is preferable (for example, the first method or the second method described later). Further, from the viewpoint of changing the texture and luster of the concave portion and the convex portion to obtain a concave-convex design having a clearer contrast, the resin composition forming the surface layer 2 is applied only to the portion (raising layer) on which the convex portion is formed. (For example, the third method described later) is preferable.

Specific examples of the method for forming the surface layer 2 having an uneven shape include the following first to third methods.

First method: A base layer 1 and other layers provided as needed are laminated in order to prepare a sheet having a layer other than the surface layer 2, and embossing is performed on the side of the sheet on which the surface layer 2 is laminated. A method of applying a curable resin composition used for forming the surface layer 2 to cure the curable resin composition.

Second method: A base layer 1 and other layers provided as needed are laminated in order to prepare a sheet having a layer other than the surface layer 2, and the surface layer 2 is on the side where the surface layer 2 of the sheet is laminated. A method of applying a curable resin composition used for forming the surface layer to cure the curable resin composition, and then embossing the surface layer 2 side.

Third method: A base layer 1 and other layers provided as needed are laminated in order to prepare a sheet having a layer other than the surface layer 2, and a convex portion on the side where the surface layer 2 of the sheet is laminated is formed. A method in which a curable resin composition used for forming the surface layer 2 is applied only to a portion to be formed to cure the curable resin composition.

On the other hand, when a resin film is used as the surface layer 2 of the second invention, the resin film is laminated on the layer located below the surface layer 2 and embossed from above the resin film. The surface layer 2 having an uneven shape can be formed.

Further, in the second invention, when the surface layer 2 is formed by using the curable resin composition, the cured product of the curable resin composition may be formed on a predetermined layer so as to have an uneven shape. , The specific method is not particularly limited. Examples of the method of imparting an uneven shape to the surface layer 2 include a method of embossing, a method of applying a resin composition forming the surface layer 2 only to a portion where a convex portion is formed, and a method of curing the surface layer 2. However, a method of embossing is preferable.

In the second invention, when the surface layer 2 is formed by using the curable resin composition, the above-mentioned first to third methods are specifically mentioned as a method for forming the surface layer 2 having an uneven shape. Be done.

In the first and second inventions, the method of applying the curable resin composition used for forming the surface layer 2 onto a predetermined layer is not particularly limited, but for example, the above-mentioned first method or the first method is used. In the case of the two methods, a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat and the like can be mentioned, and a gravure coat can be mentioned preferably. Further, in the case of the above-mentioned third method, silk screen printing, gravure printing, rotary screen printing, printing or coating method such as the molding plate cylinder method described in JP-A-2002-240078 can be mentioned.

The curable resin composition (uncured resin layer) coated on the predetermined layer in this manner is irradiated with ionizing radiation such as electron beam and ultraviolet rays to cure the resin composition, thereby forming the surface layer 2. Form. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In the irradiation of the electron beam, the higher the acceleration voltage, the higher the penetrating ability. Therefore, when a base material deteriorated by the electron beam is used as the base material layer, the transmission depth of the electron beam and the thickness of the resin layer are substantially the same. By selecting the acceleration voltage so as to be equal to each other, it is possible to suppress the irradiation of the base material layer with an extra electron beam, and it is possible to minimize the deterioration of the base material due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as a cockloft Walton type, a bandegraft type, a resonance transformer type, an insulated core transformer type, or a linear type, a dynamitron type, and a high frequency type. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

[Thermoplastic resin film layer 30]
In the first invention, the thermoplastic resin film layer 30 is a layer provided to suppress deformation or disappearance of the uneven shape of the surface layer 2 during vacuum forming or injection molding of a decorative sheet. The thermoplastic resin film layer 30 is laminated in a state where it can be peeled off from the decorative sheet (surface layer 2), and is a layer that is peeled off after being integrally molded with the molding resin.

In the present invention, "peelable" of the thermoplastic resin film layer means that the thermoplastic resin film layer can be peeled off from the surface layer having an uneven shape, and specifically, the uneven shape is not destroyed. It means that it can be peeled off. For example, when the surface layer and the thermoplastic resin film layer are peeled off by the measurement method stipulated in "10. Adhesive strength measurement 10.4.1 peeling adhesive strength to a test plate" of JIS Z0237. If the adhesive strength is about 0.01 to 20 N / 25 mm, it can be sufficiently peeled off. The adhesive strength is preferably about 0.01 to 20 N / 25 mm, more preferably about 0.02 to 10 N / 25 mm, and further preferably about 0.05 to 5 N / 25 mm. If the adhesive strength is less than 0.01 N / 25 mm, the thermoplastic resin film layer may be unexpectedly peeled off from the surface layer before or during molding of the decorative sheet, and 20 N. If it exceeds / 25 mm, the thermoplastic resin film layer is torn when the thermoplastic resin film layer is peeled off, and a part of the molding resin is formed, although it depends on the thickness of the thermoplastic resin film layer and the tensile strength of the resin. The surface layer may be crushed or deformed by remaining in the layer or a part of the surface layer being peeled off together with the thermoplastic resin film layer.

In the first invention, the thermoplastic resin film layer 30 and the surface layer 2 may be directly laminated, or another layer may be laminated between these layers. When the thermoplastic resin film layer 30 and the surface layer 2 are directly laminated, the thermoplastic resin film layer 30 becomes the unevenness protective layer 3 that protects the uneven shape of the surface layer 2.

In the first invention, when the surface layer 2 and the thermoplastic resin film layer 30 are directly laminated, the thermoplastic resin film layer 30 fills at least a part of the concave-convex concave portion of the surface layer 2. preferable. Since the thermoplastic resin film layer 30 fills the concave-convex shape of the surface layer 2, the function of protecting the uneven shape of the surface layer 2 by the thermoplastic resin film layer 30 can be further enhanced.

In the first invention, as a method of filling the concave-convex shape of the surface layer 2 with the thermoplastic resin film layer 30, for example, by extrusion molding or thermal laminating, the concave-convex shape of the surface layer 2 is filled. A method of laminating the thermoplastic resin film layer 30 can be mentioned. In the decorative sheet of the first invention, the surface layer 2 is formed of a cured product of a curable resin composition. Therefore, as compared with a decorative sheet having a thermoplastic resin film having an uneven shape on the surface, deformation of the uneven shape due to heating when the thermoplastic resin film layer 30 is laminated by thermal lamination or extrusion molding is suppressed. ing.

Further, in the decorative sheet of the first invention, since the concave-convex shape of the surface layer 2 is protected by the thermoplastic resin film layer 30, the uneven shape is protected by the resin layer made of a cured product of the curable resin. Compared to the decorative sheet, it is also excellent in moldability during injection molding and pre-molding (vacuum forming) prior to it. Further, in order to sufficiently suppress the deformation of the uneven shape and improve the workability at the time of peeling, even when the thickness of the thermoplastic resin film layer 30 is increased, the cured product of the curable resin is protected by the uneven shape. Compared to the case where it is used as, the moldability is not easily impaired. Therefore, the decorative sheet of the first invention can also be suitably used as a decorative sheet that requires high three-dimensionality formation.

In the first invention, from the viewpoint of adjusting the adhesive strength so that the thermoplastic resin film layer 30 and the surface layer 2 are brought into close contact with each other in the state of a decorative sheet and can be easily peeled off after being integrally molded with the molding resin. The thermoplastic resin film layer 30 is preferably laminated by extrusion molding.

In the first invention, when another layer is laminated between the thermoplastic resin film layer 30 and the surface layer 2, the other layer and the thermoplastic resin film layer 30 serve as the unevenness protective layer 3. Can work. Examples of other layers include the adhesive layer 31 and the release layer 32, which will be described later.

In the first invention, when the adhesive layer 31 is laminated between the thermoplastic resin film layer 30 and the surface layer 2, the uneven shape of the surface layer 2 is deformed when the thermoplastic resin film layer 30 is formed. From the viewpoint of suppressing the loss or disappearance, after forming the adhesive layer 31 described later, the thermoplastic resin film layer 30 formed in advance is laminated by the adhesive force or the adhesive force of the adhesive layer 31. Is preferable. When the adhesive layer 31 is formed of an adhesive, the adhesive layer 31 can be formed by applying an adhesive on the surface layer 2 having an uneven shape. Therefore, the formation of the adhesive layer 31 does not require extrusion molding or heating by thermal lamination. Therefore, when the adhesive layer 31 is formed of an adhesive, the thermoplastic resin film layer 30 for protecting the uneven shape of the surface layer 2 while suitably maintaining the fine uneven shape of the surface layer 2. Can be laminated.

In the first invention, the thermoplastic resin constituting the thermoplastic resin film layer 30 is not particularly limited, and is an acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as "ABS resin"); acrylonitrile-styrene-. Acrylic acid ester resin; acrylic resin; polyolefin resin such as polypropylene and polyethylene; polycarbonate resin; vinyl chloride resin; polyester resin such as polyethylene terephthalate (PET) resin and polybutylene terephthalate (PBT) resin can be mentioned. The thermoplastic resin may be contained alone or in combination of two or more.

In the first invention, when a decorative resin molded product is manufactured by an injection molding method, a so-called gate in which the surface layer and the pattern layer of the decorative sheet are melted by the high-temperature injection resin mainly at the injection site of the injection resin. It is known that a phenomenon called flow may occur and the design may be impaired. In order to reduce the gate flow, it is effective to release the heat applied to the decorative sheet to the female injection mold (the side in contact with the surface of the decorative sheet), but as in the first invention, the final In the decorative sheet, there is a thermoplastic resin film layer that is finally peeled off from the decorative resin molded product between the surface layer or the pattern layer, which is the layer remaining on the decorative resin molded product, and the female mold. In this case, the heat applied to the surface layer and the pattern layer is difficult to escape to the female mold, and there is a possibility that gate flow is likely to occur. Further, in the injection molding simultaneous decoration method, when the decorative sheet is preformed by heating and softening the decorative sheet in the mold and then vacuum sucking, the thermoplastic resin film layer is excessively softened. In some cases, the suction holes for vacuum suction provided in the female mold may be sucked into the holes to block the holes, or film debris may accumulate in the holes. From the viewpoint of suppressing these problems, the thermoplastic resin film layer is preferably a layer containing an amorphous polyester resin. Since the non-crystalline polyester resin has excellent heat resistance as compared with polyethylene or the like, it is possible to mitigate the occurrence of gate flow and suppress the thermoplastic resin film layer from being sucked into the suction holes. Further, since the non-crystalline polyester resin is more flexible than the crystalline polyester resin, the three-dimensional moldability of the decorative sheet can be ensured.

In the first invention, it is preferable to use amorphous polyethylene terephthalate (PET) as the amorphous polyester resin. As the amorphous PET, a resin generally known as A-PET or PET-G can be used.

In the first invention, the thickness of the thermoplastic resin film layer 30 is not particularly limited, but is preferably about 5 to 300 μm, and more preferably about 5 to 100 μm. As shown in FIGS. 1, 2 and 4, for example, when the uneven shape is formed by embossing, the uneven shape is effectively expressed, and a particularly excellent design feeling and feel are obtained. From the viewpoint of providing a feeling, it is preferably about 5 to 100 μm, more preferably about 20 to 50 μm. Further, the thermoplastic resin film layer 30 may be composed of a plurality of layers.

(Adhesive layer 31)
In the first invention, the adhesive layer 31 is a layer provided between the thermoplastic resin film layer 30 and the surface layer 2 as needed. The adhesive layer 31 is formed of an adhesive or an adhesive. In the first invention, when the adhesive layer 31 formed by the adhesive is laminated, the adhesive layer 31 fills the concave-convex concave portion of the surface layer 2.

In the first invention, the adhesive used for the adhesive layer 31 can be applied so as to fill the uneven shape of the surface layer 2, and the adhesive used for the surface layer 2 together with the thermoplastic resin film layer 30. As long as it can be peeled off from the surface, there is no particular limitation, and a curable resin is preferably used. Examples of the curable resin include urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, rubber-based adhesives, etc. Among them, urethane-based adhesives can maintain sufficient adhesive strength even during injection molding. It is preferable in that it can be peeled off from the surface of the surface layer 2 and the like. Examples of such urethane-based adhesives include two-component curable urethane resin-based adhesives, and two-component curable urethane resin-based adhesives include various hydroxyl groups such as polyether polyols, polyester polyols, and acrylic polyols. It is an adhesive using a two-component curable urethane resin containing a contained compound and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.

Further, in the first invention, when the pressure-sensitive adhesive is used for the pressure-sensitive adhesive layer 31, the pressure-sensitive adhesive sheet in which the pressure-sensitive adhesive is applied on the above-mentioned thermoplastic resin film layer 30 can be used. Examples of such an adhesive sheet include a general polypropylene base material coated with an acrylic adhesive.

In the first invention, the thickness of the adhesive layer 31 is not particularly limited, but is preferably about 5 to 70 μm, and more preferably about 15 to 60 μm. The thickness of the adhesive layer 31 is the thickness of the portion located above the convex portion of the layer (surface layer 2 or release layer 32) located below.

In the first invention, when the adhesive layer 31 is formed by an adhesive, the adhesive layer 31 is placed on a layer (surface layer 2 or mold release layer 32) located below the adhesive layer 31. , Can be formed by applying the above-mentioned adhesive. Specifically, the adhesive is applied to the surface of the surface layer 2 by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. (when the release layer 32 is provided, the release layer 32 It may be applied to the surface).

[Concavo-convex protective layer 3 of the second invention]
The unevenness protective layer 3 of the second invention is a layer provided on the surface layer 2 in a state of being in contact with the surface layer 2, and is laminated in a state of being peelable from the interface with the surface layer 2 and is molded. A layer that is peeled off after being integrally molded with a resin. In the second invention, the concavo-convex protective layer 3 includes an adhesive layer 31 that fills the concavo-convex-shaped recesses of the surface layer 2 and a release film layer 33 in this order from the surface layer 2 side.

In the second invention, the adhesive layer 31 of the unevenness protective layer 3 is formed by an adhesive, and can be formed by applying an adhesive on the surface layer 2 having an uneven shape. Therefore, the formation of the adhesive layer does not require extrusion molding or heating by thermal lamination as in the cushion layer disclosed in Patent Document 1 described above. Therefore, in the second invention, it is possible to form the unevenness protection layer 3 for protecting the uneven shape of the surface layer 2 while suitably maintaining the fine uneven shape of the surface layer 2.

(Adhesive layer 31 of the second invention)
As the adhesive used for the adhesive layer 31 of the unevenness protective layer 3 of the second invention, it can be applied so as to fill the uneven shape of the surface layer 2, and together with the release film layer 33, the surface layer 2 As long as it can be peeled off from the surface, there is no particular limitation, but a curable resin is preferably used. Examples of the curable resin include urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, rubber-based adhesives, etc. Among them, urethane-based adhesives can maintain sufficient adhesive strength even during injection molding. It is preferable in that it can be peeled off from the surface of the surface layer 2 and the like. Examples of such urethane-based adhesives include two-component curable urethane resin-based adhesives, and two-component curable urethane resin-based adhesives include various hydroxyl groups such as polyether polyols, polyester polyols, and acrylic polyols. It is an adhesive using a two-component curable urethane resin containing a contained compound and various polyisocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.

In the second invention, the thickness of the adhesive layer 31 is not particularly limited, but is preferably about 5 to 70 μm, and more preferably about 15 to 60 μm. The thickness of the adhesive layer 31 is the thickness of the portion located above the convex portion of the layer (surface layer 2 or release layer 32) located below.

In the second invention, the adhesive layer 31 can be formed by applying the above-mentioned adhesive on a layer (surface layer 2 or mold release layer 32) located below the adhesive layer 31. Specifically, the adhesive is applied to the surface of the surface layer 2 by a method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. (when the release layer 32 is provided, the release layer 32 It may be applied to the surface).

(Release film layer 33 of the second invention)
In the second invention, the release film layer 33 forms the concavo-convex protective layer 3 together with the adhesive layer 31 in order to suppress deformation or disappearance of the concavo-convex shape of the surface layer 2 during vacuum forming or injection molding of the decorative sheet. It is a layer provided in.

The material of the release film layer 33 of the second invention is not particularly limited, and is, for example, the same as the thermoplastic resin (including amorphous polyester resin) exemplified in the thermoplastic resin film layer 30 of the first invention. However, it can be preferably exemplified.

The thickness of the release film layer 33 of the second invention is not particularly limited, but is preferably about 5 to 100 μm, and more preferably about 20 to 50 μm.

(Release layer 32)
In the first and second inventions, the release layer 32 is a layer provided as needed for the purpose of enhancing the peelability between the thermoplastic resin film layer 30 and the surface layer 2. The release layer 32 is also provided so as to be in contact with the surface layer 2. In the present invention, when the release layer 32 is laminated, the release layer 32 fills the concave-convex concave portion of the surface layer 2. Further, when the release layer 32 and the adhesive layer 31 formed by the adhesive are laminated, in the decorative sheet of the present invention, the release layer 32 and the adhesive layer 31 are surface layers. The concave and convex concave portions of 2 are filled.

As the material for forming the release layer 32, if it can be applied so as to fill the uneven shape of the surface layer 2 and can be peeled off from the surface of the surface layer 2 together with the thermoplastic resin film layer 30. Although not particularly limited, the release layer 32 is preferably formed of a cured product of the ionizing radiation curable resin composition. This makes it possible to more effectively suppress the deformation and disappearance of the uneven shape of the surface layer 2 during vacuum forming or injection molding, and to impart an excellent design feeling and feel to the decorative resin molded product.

<Ionizing radiation curable resin in release layer 32>
The type, preferred, and the like of the ionizing radiation curable resin used for forming the release layer 32 are the same as those used for forming the surface layer 2. In particular, among the ionizing radiation resins, the combination of the ionizing radiation curable resin (1) and the ionizing radiation curable resin (2) exemplified in the column of surface layer 2 is a surface layer during vacuum forming or injection molding. It is preferably used in the release layer 32 because it can provide not only the action of suppressing the deformation and disappearance of the uneven shape of No. 2 but also the ease of peeling when peeling after being integrally molded with the molding resin. As the ionizing radiation curable resin in the release layer 32, trifunctional pentaerythritol acrylate is preferable. Further, the ionizing radiation curable resin used for forming the release layer 32 and the ionizing radiation curable resin used for forming the surface layer 2 may be of the same type or different types. ..

<Other additive ingredients>
The ionizing radiation curable resin composition used for forming the release layer 32 contains, if necessary, other resin components in order to improve moldability and the like, in addition to the ionizing radiation curable resin. You may. Examples of the resin component other than the ionizing radiation curable resin include acrylic resin; polyvinyl acetal (butyral resin) such as polyvinyl butyral; polyester resin such as polyethylene terephthalate and polybutylene terephthalate; vinyl chloride resin; urethane resin; polyethylene. , Polypropylene and other polyolefins; Polystyrene, α-Methylstyrene and other styrene resins; Polyamides; Polycarbonate; Polyoxymethylene and other acetal resins; Ethylene-4 fluoride ethylene copolymer and other fluororesins; Acetal resin; examples thereof include thermoplastic resins such as liquid crystal polyester resins. These resin components may be used alone or in combination of two or more.

In addition to the ionizing radiation curable resin composition, the release layer 32 includes a silicone resin, a fluorine resin, an acrylic resin (for example, an acrylic-melamine resin is included), a polyester resin, a polyolefin resin, and a polystyrene. Thermoplastic resins such as based resins, polyurethane resins, cellulose resins, vinyl chloride-vinyl acetate copolymer resins, nitrified cotton, copolymers of monomers forming the thermoplastic resins, or these resins (meth). ) A resin composition modified with acrylic acid or urethane can be formed alone or by using a mixture of a plurality of resins. Among them, acrylic resins, polyester resins, polyolefin resins, polystyrene resins, copolymers of monomers forming these resins, and urethane-modified products thereof are preferable, and more specifically, acrylic-melamine. A resin composition alone, an acrylic-melamine resin-containing composition, a resin composition obtained by mixing a polyester resin with a urethane-modified copolymer of ethylene and acrylic acid, and a copolymer of an acrylic resin and styrene and acrylic. Examples thereof include a resin composition in which the above emulsion is mixed. Of these, it is particularly preferable to form the release layer 32 with the acrylic-melamine resin alone or a composition containing 50% by mass or more of the acrylic-melamine resin.

Various additives can be added to the resin composition forming the release layer 32 in consideration of the desired physical properties to be provided in the release layer 32. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesiveness improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a coloring agent. These additives can be appropriately selected and used from those commonly used. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

The thickness of the release layer 32 is not particularly limited, but is preferably about 1 to 40 μm, and more preferably about 5 to 15 μm. The thickness of the release layer 32 is the thickness of the portion located above the convex portion of the surface layer 2.

The release layer 32 can be formed by applying the above-mentioned resin composition on the surface layer 2. Specifically, the resin composition may be applied to the surface of the surface layer 2 by a method such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating.

[Primer layer 4]
In the first and second inventions, the primer layer 4 is a pattern layer between the base layer layer 1 and the surface layer 2 for the purpose of making it difficult for fine cracks and whitening to occur in the stretched portion of the surface layer 2. When 5 is provided, it is a layer provided as needed between the pattern layer 5 and the surface layer 2 and / or between the base layer 1 and the pattern layer 5.

From the viewpoint of improving the adhesion between the surface layer 2 and the layer located below it, a primer is directly below the surface layer 2 (or directly below the resin layer 7 when the resin layer 7 is formed of a curable resin). It is preferable that the layer 4 is provided.

Examples of the primer composition constituting the primer layer 4 include urethane resin, (meth) acrylic resin, (meth) acrylic-urethane copolymer resin, vinyl chloride-vinyl acetate copolymer, polyester resin, butyral resin, and chlorinated polypropylene. , Chlorinated polyethylene or the like as a binder resin is preferably used, and these resins can be used alone or in admixture of two or more. Among these, urethane resin, (meth) acrylic resin, and (meth) acrylic-urethane copolymer resin are preferable.

As the urethane resin, polyurethane containing a polyol (polyhydric alcohol) as a main component and an isocyanate as a cross-linking agent (curing agent) can be used. As the polyol, those having two or more hydroxyl groups in the molecule, for example, polyester polyol, polyethylene glycol, polypropylene glycol, acrylic polyol, polyether polyol and the like are used. Examples of the isocyanate include polyvalent isocyanate having two or more isocyanate groups in the molecule, aromatic isocyanate such as 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Etc., an aliphatic (or alicyclic) isocyanate is used. It is also possible to mix urethane resin and butyral resin.

Acrylic polyol or polyester polyol as a polyol, hexamethylene diisocyanate as a cross-linking agent, from the viewpoints of adhesion to the surface layer 2 after cross-linking, difficulty in causing interaction after laminating the surface layer 2, physical properties, and moldability. It is preferable to combine it with 4,4-diphenylmethane diisocyanate, and it is particularly preferable to use an acrylic polyol and hexamethylene diisocyanate in combination.

The (meth) acrylic resin is a homopolymer of (meth) acrylic acid ester, a copolymer of two or more different (meth) acrylic acid ester monomers, or a combination of (meth) acrylic acid ester and another monomer. Polymers include, specifically, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate- (Meta) butyl acrylate copolymer, ethyl (meth) acrylate- (meth) butyl acrylate copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl acrylate copolymer A (meth) acrylic resin composed of a single polymer or a copolymer containing the (meth) acrylic acid ester such as the above is preferably used.

As the (meth) acrylic-urethane copolymer resin, for example, an acrylic-urethane (polyester urethane) block copolymer resin is preferable. As the curing agent, the above-mentioned various isocyanates are used. For the acrylic-urethane (polyester urethane) block copolymer resin, the acrylic / urethane ratio (mass ratio) is preferably adjusted in the range of 9/1 to 1/9, more preferably 8/2 to 2/8, if desired. Is preferable.

The thickness of the primer layer 4 is not particularly limited, but is, for example, about 0.5 to 20 μm, preferably 1 to 5 μm.

The primer layer 4 uses a primer composition, a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, a solid coat with a silk screen, a wire bar coat, and the like. It is formed by a normal coating method such as a flow coat, a comma coat, a flow coat, a brush coat, a spray coat, or a transfer coating method. Here, the transfer coating method is a method in which a coating film of a primer layer or an adhesive layer is formed on a thin sheet (film base material), and then the surface of the target layer in the decorative sheet is coated.

[Pattern layer 5]
In the first and second inventions, the pattern layer 5 is used between the base layer 1 and the surface layer 2 or the surface layer of the base layer 1 as necessary for the purpose of imparting decorativeness to the decorative sheet. It can be provided on the opposite side of 2. When the primer layer 4 is provided, it can be provided between the base layer 1 and the primer layer 4, or when the concealing layer is provided, between the concealing layer and the surface layer 2, etc., if necessary. As shown in FIG. 6, the pattern layer 5 may be provided in a plurality of layers.

The pattern layer 5 can be, for example, a layer in which a desired pattern is formed by using an ink composition. As the ink composition used for forming the pattern layer 5, a binder in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent or the like is appropriately mixed is used. ..

The binder used in the ink composition is not particularly limited, and for example, polyurethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin. , Polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin and the like. These binders may be used alone or in combination of two or more.

The colorant used in the ink composition is not particularly limited, but for example, carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine blue, cobalt blue. Inorganic pigments such as; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthaloanine blue; metal pigments composed of scaly foil pieces such as aluminum and brass; scaly such as titanium dioxide-coated mica and basic lead carbonate. Examples include pearl luster (pearl) pigments made of foil pieces.

The pattern formed by the pattern layer 5 is also not particularly limited, but for example, a stone pattern imitating the surface of a rock such as a wood grain pattern or a marble pattern (for example, a travertin marble pattern), or a cloth grain or a cloth-like pattern is imitated. Examples thereof include a fabric pattern, a tiled pattern, a brick pile pattern, and the like, which may be a pattern such as a parquet or a patchwork in which these are combined, or a solid color (so-called solid color). These patterns are formed by multicolor printing with ordinary yellow, red, blue, and black process colors, but they can also be printed with special colors by preparing plates of the individual colors that make up the pattern. Can be formed.

The thickness of the pattern layer is not particularly limited, and examples thereof include 1 to 30 μm, preferably 1 to 20 μm.

Further, the pattern layer 5 may be a metal thin film layer. Examples of the metal forming the metal thin film layer include tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of them. The method for forming the metal thin film layer is not particularly limited, and examples thereof include a vapor deposition method such as a vacuum vapor deposition method, a sputtering method, and an ion plating method using the above-mentioned metal. The metal thin film layer may be provided on the entire surface or may be provided partially. Further, in order to improve the adhesion with the adjacent layer, a primer layer using a known resin may be provided on the front surface or the back surface of the metal thin film layer.

[Concealment layer]
In the first and second inventions, the concealing layer is based on the case where the primer layer 4 is provided between the base layer 1 and the surface layer 2 for the purpose of suppressing the color change and variation of the base layer 1. It is a layer provided as needed between the material layer 1 and the primer layer 2, or between the base material layer 1 and the pattern layer 5 when the pattern layer 5 is provided.

Since the concealing layer is provided to suppress the base material layer from adversely affecting the color tone and the pattern of the decorative sheet, it is generally formed as an opaque color layer.

The concealing layer is formed by using an ink composition in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent or the like is appropriately mixed in a binder. The ink composition forming the concealing layer is appropriately selected and used from those used for the above-mentioned pattern layer.

The concealing layer is usually set to a thickness of about 1 to 20 μm, and it is desirable that the concealing layer is formed as a so-called solid printing layer.

The concealing layer is a usual printing method such as gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, inkjet printing; gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll. It is formed by a normal coating method such as a coat.

[Transparent resin layer 6]
In the first and second inventions, the transparent resin layer 6 is the base material layer 1 when the primer layer 4 is provided between the base material layer 1 and the surface layer 2 for the purpose of improving chemical resistance and scratch resistance. When the primer layer 4 and the pattern layer 5 are provided between the primer layer 4 and the pattern layer 5, or between the pattern layer 5 and the surface layer 2, or when the primer layer 4 and the pattern layer 5 are provided on the base material layer 1 in this order, the primer layer 4 and the pattern layer are provided. It is a layer provided as needed, such as between 5. The transparent resin layer 6 is a layer preferably provided in a decorative sheet integrated with a molding resin by an insert molding method.

The resin component forming the transparent resin layer 6 is appropriately selected according to transparency, three-dimensional moldability, shape stability, chemical resistance, etc., but a thermoplastic resin is usually used. The thermoplastic resin is not particularly limited, but for example, a polyolefin resin such as acrylic resin, polypropylene, or polyethylene, a polycarbonate resin, an ABS resin, a polyester resin such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), or a vinyl chloride resin. Etc. are used. Among these thermoplastic resins, from the viewpoint of chemical resistance, scratch resistance, etc., preferably acrylic resin, polyolefin resin, polycarbonate resin, polyester resin; more preferably acrylic resin, polyester resin; more preferably polyester. Resin is mentioned.

The transparent resin layer 6 is subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one or both sides, if necessary, in order to improve the adhesion with the other layers in contact with the transparent resin layer 6. You may. These physical or chemical surface treatments are similar to the surface treatments applied to the substrate layer.

The thickness of the transparent resin layer 6 is not particularly limited, and examples thereof include 10 to 200 μm, preferably 15 to 150 μm.

The transparent resin layer 6 may be laminated via an adhesive, or may be directly laminated without an adhesive. When laminating via an adhesive, examples of the adhesive used include polyester resin, polyether resin, polyurethane resin, epoxy resin, phenol resin resin, polyamide resin, polyolefin resin, and poly. Examples thereof include vinyl acetate-based resins, cellulose-based resins, (meth) acrylic-based resins, polyimide-based resins, amino resins, rubbers, and silicon-based resins. Further, when laminating without using an adhesive, it can be carried out by a method such as an extrusion method, a sand ramming method, or a thermal laminating method.

[Resin layer 7]
In the first invention, the resin layer 7 is directly below the surface layer 2 (with the thermoplastic resin film layer 30), if necessary, for the purpose of improving the scratch resistance, weather resistance, etc. of the decorative resin molded product. Is a layer provided on the opposite side). The resin layer 7 is preferably formed when the uneven shape of the surface layer 2 is formed by a partially provided convex portion and a concave portion in which the lower layer of the surface layer 2 is exposed between the convex portions. It is provided.

The resin forming the resin layer 7 of the first invention is not particularly limited, and examples thereof include a curable resin and a thermoplastic resin. Examples of the curable resin include thermosetting resins and ionizing radiation curable resins, and ionizing radiation curable resins are preferable. Specific examples of the thermosetting resin and the ionizing radiation curable resin include the same ones as those exemplified in the above-mentioned [Surface layer 2]. Further, as the thermoplastic resin, the same ones as those exemplified in the above-mentioned [Thermoplastic resin film layer 30] can be exemplified. When the resin layer 7 is a thermoplastic resin, a thermoplastic resin film can be preferably used as the resin layer 7.

When the resin layer 7 is provided, it is directly below the resin layer 7 (on the opposite side of the surface layer 2), if necessary, for the purpose of improving the adhesion between the resin layer 7 and the layer located below the resin layer 7. , An adhesive layer (not shown) may be provided. In particular, when a thermoplastic resin film is used as the resin layer 7, it is preferable to provide an adhesive layer. Examples of the resin forming the adhesive layer include the same resins as those exemplified in [Backside Adhesive Layer] described later.

The thickness of the resin layer 7 is not particularly limited, and examples thereof include 30 to 300 μm μm, preferably 50 to 200 μm.

[Backside adhesive layer]
In the first and second inventions, the transparent back surface adhesive layer (not shown) is the back surface (front surface) of the base material layer 1 for the purpose of improving the adhesion with the molding resin when molding the decorative resin molded product. A layer provided on the surface opposite to the layer 2 as needed.

A thermoplastic resin or a curable resin is used for the back surface adhesive layer, depending on the molding resin used for the decorative resin molded product.

Examples of the thermoplastic resin used for forming the back surface adhesive layer include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride / vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, and polyamide. Examples include resins and rubber-based resins. These thermoplastic resins may be used alone or in combination of two or more.

Examples of the thermosetting resin used for forming the back surface adhesive layer include urethane resin and epoxy resin. These thermosetting resins may be used alone or in combination of two or more.

Method for Manufacturing Decorative Sheet The decorative sheet of the first invention can be manufactured, for example, through the following steps 1A and 2A.

The first step A of forming a laminated body having a concavo-convex shape and having a surface layer formed of a cured product of a curable resin composition laminated on the base material layer.
A second A step of forming a peelable thermoplastic resin film layer on the surface layer of the laminate obtained in the first A step.

In the first step and the second step of the first invention, the components used for forming each layer, the specific conditions of the forming method of each layer, the method of forming the uneven shape of the surface layer 2 and the like are described in the composition of each layer. As mentioned in the column.

When the other layers (adhesive layer 31, release layer 32, etc.) described above are not laminated on the surface layer 2, the second A step can be performed by, for example, the following steps.
A step of forming a peelable thermoplastic resin film layer on the surface layer 2 by extrusion molding or heat laminating so as to fill the uneven concave portions of the surface layer 2.

Further, when the adhesive layer 31 formed by the adhesive and the thermoplastic resin film layer 30 are laminated on the surface layer 2, the second A step can be performed by, for example, the following steps.
A step of applying a resin composition constituting an adhesive on the surface layer 2 to fill the concave-convex concave portions of the surface layer 2 to form the adhesive layer 31.
A step of laminating a peelable thermoplastic resin film layer 30 on the adhesive layer 31.

When the release layer 32 and the thermoplastic resin film layer 30 are laminated on the surface layer 2, the second A step can be performed by, for example, the following steps.
A step of applying the resin composition constituting the release layer 32 on the surface layer 2 and filling the concave-convex concave portions of the surface layer 2 to form the release layer 32.
A step of laminating a peelable thermoplastic resin film layer 30 on the release layer 32.

Further, when the release layer 32, the adhesive layer 31 and the thermoplastic resin film layer 30 are laminated on the surface layer 2, the second A step can be performed by, for example, the following steps. ..
A step of applying the resin composition constituting the release layer 32 on the surface layer 2 and filling the concave-convex concave portions of the surface layer 2 to form the release layer 32.
A step of applying a resin composition constituting an adhesive on the release layer 32 to fill the concave-convex concave portions of the surface layer 2 to form the adhesive layer 31.
A step of laminating a thermoplastic resin film layer 30 on the adhesive layer 31.

On the other hand, the decorative sheet of the second invention can be produced, for example, through the following steps 1B to 3B.

First B step of preparing the surface layer 2 having an uneven shape A second B step of applying an adhesive on the surface layer 2 so as to fill the concave and convex concave portions of the surface layer 2 and laminating the adhesive layer 31. The third B step of laminating the release film layer 33 on the surface.

In the first to third B steps, the components used for forming each layer, the specific conditions for forming each layer, the method for forming the uneven shape of the surface layer 2, and the like are as described in the column of composition of each layer. Is.

Further, when the unevenness protective layer 3 is formed by the laminate of the release layer 32, the adhesive layer 31, and the release film layer 33, the second B step and the third B step can be performed by, for example, the following steps.
A step of applying the resin composition constituting the release layer 32 on the surface layer 2 and filling the concave-convex concave portions of the surface layer 2 to form the release layer 32.
A step of applying an adhesive on the release layer 32 to fill the uneven concave portions of the surface layer 2 to form the adhesive layer 31.
A step of laminating the release film layer 33 on the adhesive layer 31.

When the surface layer 2 is formed of a resin film, the first B step can be performed by, for example, the following steps.
The process of preparing the surface layer 2 made of a resin film and
A step of embossing from above the surface layer 2 to form an uneven shape on the surface of the surface layer 2.

In this case, when another layer such as the pattern layer 5 and the primer layer 4 is formed between the base material layer 1 and the surface layer 2, the following steps can be performed.
A step of laminating other layers such as the pattern layer 5 and the primer layer 4 on the base material layer 1 A step of laminating a surface layer 2 made of a resin film on the other layers such as the pattern layer 5 and the primer layer 4. A step of embossing from above the surface layer 2 to form an uneven shape on the surface of the surface layer 2.

2. The thermoplastic resin film layer with a decorative resin molded article first and thermoplastic resin film layer with a decorative resin molded article of the second invention, respectively, integrally molded resin decorative sheet of the first and second aspects of the invention It is formed by making it into a plastic. That is, in the decorative resin molded product with the thermoplastic resin film layer of the first invention, at least the molding resin layer 8, the base material layer 1, the surface layer 2 having an uneven shape, and the thermoplastic resin film layer 30 are laminated in this order. The surface layer 2 is characterized in that it is formed of a cured product of a curable resin composition. FIGS. 7 and 8 show the cross-sectional structure of one aspect of the decorative resin molded product with the thermoplastic resin film layer of the first invention.

Further, in the decorative resin molded product with the unevenness protective layer of the second invention, at least the molding resin layer 7, the surface layer 2 having the uneven shape, and the peelable unevenness protective layer 3 are laminated in this order, and the unevenness is formed. The protective layer 3 is characterized in that it includes an adhesive layer 31 that fills the concave-convex concave portions of the surface layer 2 and a release film layer 33 in this order from the surface layer 2 side. FIG. 15 shows a cross-sectional structure of one aspect of the decorative resin molded product with the unevenness protective layer of the second invention.

The decorative resin molded product with a thermoplastic resin film layer of the present invention (first and second inventions) forms a molded resin layer by injecting a resin onto the base material layer side of the decorative sheet of the present invention. It can be manufactured by a method comprising a process. Specifically, the decorative sheet of the present invention is produced by various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method. By applying the decorative sheet of the present invention to various injection molding methods to produce a decorative resin molded product with a thermoplastic resin film layer, the above-mentioned effect of suppressing the uneven shape from being impaired during injection molding can be obtained. As a suitable example of the molding resin layer 8 constituting the decorative resin molded product with the thermoplastic resin film layer of the present invention, there is an injection resin layer formed by injection molding. Among these injection molding methods, an insert molding method and an injection molding simultaneous decoration method are preferably mentioned.

In the insert molding method, first, in the vacuum forming step, the decorative sheet of the present invention is vacuum-formed (offline pre-molding) into the surface shape of the molded product in advance by a vacuum forming mold, and then the excess portion is trimmed if necessary. Obtain a molded sheet. This molding sheet is inserted into an injection molding mold, the injection molding mold is molded, the fluid resin is injected into the mold and solidified, and at the same time as the injection molding, the base of the decorative sheet is applied to the outer surface of the resin molded product. By integrating the material layer 1 side, a decorative resin molded product with a thermoplastic resin film layer is manufactured.

More specifically, the decorative resin molded product with the thermoplastic resin film layer of the present invention is produced by an insert molding method including the following steps.

A vacuum forming step of forming the decorative sheet of the present invention into a three-dimensional shape in advance using a vacuum forming mold.
The process of trimming the excess part of the vacuum-formed decorative sheet to obtain a molded sheet, and the molding sheet obtained in the above step is inserted into an injection molding mold, the injection molding mold is closed, and the resin in a fluid state is molded. The process of injecting into the inside to integrate the resin and the molded sheet.

In the vacuum forming step in the insert molding method, the decorative sheet may be heated for molding.
The heating temperature at this time is not particularly limited and may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like. For example, when an ABS resin film is used as the base material layer. For example, it can be usually about 100 to 250 ° C., preferably about 130 to 200 ° C. Further, in the integration step, the temperature of the resin in the flowing state is not particularly limited, but can be usually about 180 to 320 ° C., preferably about 220 to 280 ° C.

Further, in the injection molding simultaneous decoration method, the decoration sheet of the present invention is placed in a female mold that also serves as a vacuum molding mold provided with injection molding suction holes, and pre-molding (in-line pre-molding) is performed with this female mold. After that, the injection molding mold is molded, the fluid resin is injection-filled in the mold and solidified, and at the same time as the injection molding, the base material layer of the decorative sheet of the present invention is applied to the outer surface of the resin molded product. By integrating one side, a decorative resin molded product with a thermoplastic resin film layer is manufactured.

More specifically, the decorative resin molded product with the thermoplastic resin film layer of the present invention is produced by the injection molding simultaneous decoration method including the following steps.

The decorative sheet of the present invention is installed so that the base material of the decorative sheet faces the molded surface of a movable mold having a molded surface having a predetermined shape, and then the decorative sheet is heated and softened. At the same time, a step of pre-molding the decorative sheet by vacuum suctioning from the movable mold side and bringing the softened decorative sheet into close contact with the molding surface of the movable mold.
After the movable mold having the decorative sheet adhered along the molding surface and the fixed mold are molded, a fluid resin molding material is injected and filled into the cavity formed by both molds. An injection molding process in which the formed resin molded body and the decorative sheet are laminated and integrated by solidification, and a resin molded body in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. The process of taking out.

In the premolding process of the injection molding simultaneous decoration method, the heating temperature of the decoration sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decoration sheet, the thickness of the decoration sheet, and the like. When a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can usually be about 70 to 130 ° C. Further, in the injection molding step, the temperature of the resin in the fluid state is not particularly limited, but can be usually about 180 to 320 ° C., preferably about 220 to 280 ° C.

Further, the decorative resin molded product of the present invention is prepared by a decoration method such as a vacuum crimping method in which the decorative sheet of the present invention is attached onto a three-dimensional resin molded body (molded resin layer) prepared in advance. Can also be produced.

In the vacuum crimping method, first, the decorative sheet and the resin molded body of the present invention are placed in a vacuum crimping machine including a first vacuum chamber located on the upper side and a second vacuum chamber located on the lower side. Installed in the vacuum crimping machine so that the vacuum chamber side and the resin molded body are on the second vacuum chamber side and the base material layer 1 side of the decorative sheet faces the resin molded body side, and the two vacuum chambers are in a vacuum state. do. The resin molded body is installed on an elevating table that can be raised and lowered up and down, which is provided on the second vacuum chamber side. Next, while pressurizing the first vacuum chamber, the molded body is pressed against the decorative sheet using an elevating table, and the resin molded body is stretched while stretching the decorative sheet by utilizing the pressure difference between the two vacuum chambers. Stick on the surface of. Finally, the decorative resin molded product of the present invention can be obtained by opening the two vacuum chambers to atmospheric pressure and trimming the excess portion of the decorative sheet as needed.

In the vacuum crimping method, it is preferable to include a step of heating the decorative sheet in order to soften the decorative sheet and improve moldability before the step of pressing the molded body against the decorative sheet. The vacuum crimping method including this step is sometimes called a vacuum heating crimping method in particular. The heating temperature in the step may be appropriately selected depending on the type of resin constituting the decorative sheet, the thickness of the decorative sheet, and the like, but when a polyester resin film or an acrylic resin film is used as the base material layer, Usually, it can be about 60 to 200 ° C.

In the decorative resin molded product with the thermoplastic resin film layer of the present invention, the molding resin layer may be formed by selecting a molding resin according to the intended use. The molding resin may be a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin used as the molding resin include polyolefin resins such as polyethylene and polypropylene, ABS resin, styrene resin, polycarbonate resin, acrylic resin, vinyl chloride resin and the like. These thermoplastic resins may be used alone or in combination of two or more.

Examples of the thermosetting resin used as the molding resin include urethane resin and epoxy resin. These thermosetting resins may be used alone or in combination of two or more.

A decorative resin molded product can be obtained by peeling and removing the thermoplastic resin film layer from the decorative resin molded product with the thermoplastic resin film layer of the present invention. Further, in the decorative resin molded product with the thermoplastic resin film layer, the thermoplastic resin film layer serves as a protective sheet for the decorative resin molded product, so that it can be stored as it is without being peeled off after production. Occasionally, the thermoplastic resin film layer may be peeled off. By using it in such an embodiment, it is possible to prevent the decorative resin molded product from being scratched due to rubbing during transportation or the like.

3. 3. Decorative resin molded product In the first invention, a decorative resin molded product having an uneven shape on the surface is imparted by peeling and removing the thermoplastic resin film layer 30 from the decorative resin molded product with a thermoplastic resin film layer. Is obtained. Further, when another layer such as the adhesive layer 31 or the release layer 32 is laminated between the thermoplastic resin film layer 30 and the surface layer 2, the other layer is also referred to as the thermoplastic resin film layer 30. At the same time, it is peeled off. When the thermoplastic resin film layer 30 is peeled off and removed from the decorative resin molded product with the thermoplastic resin film layer, the surface layer 2 appears on the surface of the decorative resin molded product, and the uneven shape gives an excellent design and feel. It is revealed. 10 and 11 show the cross-sectional structure of one aspect of the decorative resin molded product in which the thermoplastic resin film layer 30 is removed from the decorative resin molded product with the thermoplastic resin film layer shown in FIGS. 7 and 8, respectively. ..

Further, in the second invention, by peeling and removing the unevenness protective layer 3 from the decorative resin molded product with the unevenness protective layer, a decorative resin molded product having an uneven shape on the surface can be obtained. When the support is peeled off and removed from the decorative resin molded product with the concavo-convex protective layer, the surface layer 2 appears on the surface of the decorative resin molded product, and the uneven shape gives an excellent design and feel. FIG. 16 shows a cross-sectional structure of one aspect of the decorative resin molded product from which the unevenness protective layer 3 has been removed in the second invention.

The decorative resin molded products of the first and second inventions have an excellent design feeling and a feeling of touch due to the uneven shape. Therefore, for example, the interior or exterior material of a vehicle such as an automobile; skirting board, rim Such as building members; fittings such as window frames and door frames; interior materials for buildings such as walls, floors and ceilings; housings for home appliances such as television receivers and air conditioners; can be used as containers and the like.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

[Manufacturing of decorative sheets]
Example 1A
An ABS resin film (thickness 200 μm) was used as the base material layer. A wood grain pattern layer (thickness 5 μm) was formed by gravure printing on the base material layer using an ink composition containing an acrylic resin. Resin composition for primer layer containing a binder resin composed of a two-component curable resin containing 100 parts by mass of a main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts by mass of a curing agent (hexamethylene diisocyanate) on the pattern layer. A material was applied and dried to form a primer layer having a thickness of 2 μm, and a laminate in which a base material layer / a pattern layer / a primer layer was laminated in this order was obtained.

The primer layer side of the laminate obtained above was embossed to form a dot-patterned uneven shape on the primer layer. The embossing plate depth (height from the bottom of the concave portion to the upper surface of the convex portion) of the embossed plate used for the embossing is 60 μm. Next, the ionizing radiation curable resin composition (EB1) described later was applied onto the primer layer on which the uneven shape was formed so that the thickness after curing was 8 μm. This resin composition was cured by irradiating the resin composition with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) to form a surface layer having an uneven shape.

Next, by forming a polyethylene layer on the surface layer by extrusion molding, a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape / a thermoplastic resin film layer (polyethylene film) are laminated in this order. A decorative sheet having a laminated structure was obtained. As the conditions for extrusion molding, the temperature under the die of the extruder was 230 to 250 ° C., and the thickness of the polyethylene layer was 50 μm.

Example 2A
In the same manner as in Example 1A, a surface layer having an uneven shape was formed on a laminated body in which a base material layer / a pattern layer / a primer layer were laminated in this order. Next, except that a polyethylene film (thickness 30 μm) as a thermoplastic resin film layer was laminated on the surface layer and the surface layer and the thermoplastic resin film layer were adhered by a thermal lamination method, the same as in Example 1A. Similarly, a decorative sheet having a laminated structure in which a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape / a thermoplastic resin film layer were laminated in this order was obtained. The conditions of the thermal lamination method were a heating temperature of 200 to 230 ° C., a pressure of 5 kgf, and a polyethylene film thickness of 50 μm.

Example 3A
The ionizing radiation curable resin composition forming the surface layer has a base material layer / pattern layer / primer layer / uneven shape in the same manner as in Example 1A, except that EB2 described later is used instead of EB1. A decorative sheet having a laminated structure in which a surface layer / a thermoplastic resin film layer was laminated in order was obtained.

Example 4A
A laminate in which the base material layer / pattern layer / primer layer are laminated in this order in the same manner as in Example 1A, except that EB2 is used instead of EB1 as the ionizing radiation curable resin composition forming the surface layer. A surface layer having an uneven shape was formed on the surface. Next, the ionizing radiation curable resin composition (EB3) described later was applied onto the surface layer so that the thickness after curing was 10 μm. This resin composition was irradiated with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) to cure it, and a release layer was formed on the surface layer. Next, an adhesive made of a polyester resin composition is applied onto the release layer so that the thickness after curing is 30 μm, and the concave-convex concave portion of the surface layer is filled with the adhesive layer. Was formed. Next, a thermoplastic resin film layer (polyethylene film, thickness 30 μm) is laminated on the adhesive layer, and the base material layer / pattern layer / primer layer / surface layer having uneven shape / release layer / A decorative sheet having a laminated structure in which an adhesive layer / a thermoplastic resin film layer was laminated in this order was obtained.

Comparative Example 1A
An acrylic resin film (thickness 75 μm) was used as the surface layer. A wood grain pattern layer (thickness 5 μm) was formed on the surface layer by gravure printing using an ink composition containing an acrylic resin. An ABS resin film (thickness 200 μm) as a base material layer was laminated on the pattern layer. Next, the surface of the obtained laminate on the surface layer side was embossed using the same embossing plate as in Example 1A to form an uneven shape of a dot pattern on the surface layer. Next, as in Example 1A, a thermoplastic resin film layer (polyethylene layer) is formed on the surface layer having an uneven shape by extrusion molding, and the base material layer / pattern layer / surface layer having an uneven shape / heat. A decorative sheet having a laminated structure in which plastic resin film layers were laminated in order was obtained.

Example 5A
An ABS resin film (thickness 400 μm) was used as the base material layer. A wood grain pattern layer (thickness 5 μm) was formed by gravure printing on the base material layer using an ink composition containing an acrylic resin. Resin composition for primer layer containing a binder resin composed of a two-component curable resin containing 100 parts by mass of a main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts by mass of a curing agent (hexamethylene diisocyanate) on the pattern layer. A material was applied and dried to form a primer layer having a thickness of 2 μm, and a laminate in which a base material layer / a pattern layer / a primer layer was laminated in this order was obtained. Next, the ionizing radiation curable resin composition (UV) described later was printed by screen printing so as to have a coating thickness of 30 μm with dots having a diameter of 2 mm. The uncured resin layer was irradiated with ultraviolet rays having an integrated light intensity of 600 mJ / cm ² , and the ionizing radiation curable resin was cured to form a surface layer having an uneven shape. Next, by forming a polyethylene layer on the surface layer by extrusion molding, a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape / a thermoplastic resin film layer (polyethylene film) are laminated in this order. A decorative sheet having a laminated structure was obtained. As the conditions for extrusion molding, the temperature under the die of the extruder was 230 to 250 ° C., and the thickness of the polyethylene layer was 50 μm.

Example 6A
In the same manner as in Example 5A, a laminate in which the base material layer / pattern layer / primer layer was laminated in this order was obtained. Next, the ionizing radiation curable resin composition (EB3) described later was coated on the primer layer by bar coating so that the thickness after curing was 10 μm. The uncured resin layer was provided with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad). Next, a surface layer having an uneven shape and a thermoplastic resin film layer are formed on the resin layer in the same manner as in Example 5A, and have a base material layer / pattern layer / primer layer / resin layer / uneven shape. A decorative sheet having a laminated structure in which a surface layer / a thermoplastic resin film layer (polyethylene film) was laminated in this order was obtained.

Example 7A
A 75 μm thick uncolored transparent acrylic resin sheet containing polymethylmethacrylate as the main component is used as the resin layer, and an adhesive layer (thickness) composed of polymethylmethacrylate and a two-component curable urethane resin-based adhesive is formed on the back surface of the resin layer. 10 μm) and wood grain pattern layer (thickness 5 μm) are sequentially laminated, and then a base material layer made of ABS resin (thickness 400 μm) is laminated on the pattern layer by dry lamination, and the base material layer / pattern layer is laminated. A laminate in which the / adhesive layer / resin layer was laminated in this order was obtained. Next, in the same manner as in Example 5A, a surface layer having an uneven shape and a thermoplastic resin film layer are formed, and a base material layer / a pattern layer / an adhesive layer / a resin layer / a surface layer having an uneven shape / thermoplastic. A decorative sheet having a laminated structure in which resin film layers (polyethylene films) were laminated in order was obtained.

Example 8A
In the same manner as in Example 5A, a laminated body in which a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape was laminated in this order was obtained. Next, by laminating an A-PET film on the surface layer by extrusion molding, a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape / a thermoplastic resin film layer (A-PET) can be formed. A decorative sheet having a laminated structure, which was laminated in order, was obtained. As the conditions for extrusion molding, the temperature under the die of the extruder was 250 to 260 ° C., and the thickness of the PET layer was 50 μm.

Comparative Example 2A
A decorative sheet having a laminated structure in which a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape was laminated in this order was obtained in the same manner as in Example 5A except that the thermoplastic resin film layer was not formed. ..

Comparative Example 3A
A decorative sheet having a laminated structure in which a base material layer / a pattern layer / a primer layer / a resin layer / a surface layer having an uneven shape are laminated in this order is the same as in Example 6A except that a thermoplastic resin film layer is not formed. Obtained.

Comparative Example 4A
Decoration of a laminated structure in which a base material layer / a pattern layer / an adhesive layer / a resin layer / a surface layer having an uneven shape are laminated in this order in the same manner as in Example 7A except that a thermoplastic resin film layer is not formed. I got a sheet.

[Manufacturing of decorative resin molded products]
Each decorative sheet was heated to 160 ° C. with an infrared heater to soften it. Next, vacuum forming was performed using a vacuum forming mold (maximum draw ratio 100%), and premolding was performed so as to follow the internal shape of the mold and the mold was compacted. Then, a mixed resin of polycarbonate and ABS was injected into the cavity of the mold, and the decorative sheet and the molding resin were integrally molded to obtain a decorative resin molded product with a thermoplastic resin film layer. Next, the thermoplastic resin film layer was manually peeled off from the obtained decorative resin molded product with the thermoplastic resin film layer to obtain a decorative resin molded product. In the decorative sheets of Examples 1A to 8A and Comparative Example 1A, since the layer for protecting the uneven shape of the surface layer was a thermoplastic resin film layer, both were excellent in three-dimensional moldability.

<Evaluation of uneven shape of decorative sheet>
In the manufacturing process of the decorative sheet of Examples and Comparative Examples, the unevenness of the surface layer before and after forming the thermoplastic resin film layer was visually and touch-evaluated. The thermoplastic resin film layer was peeled off from the decorative sheet by manually peeling the thermoplastic resin film layer from the decorative sheet. The evaluation criteria are as follows. The results are shown in Tables 1A and 2A.
〇: There is almost no change in the unevenness.
Δ: The unevenness changed, but even if the thermoplastic resin film layer was formed and then peeled off, the unevenness was felt.
X: The unevenness is greatly changed, and the unevenness is not felt after the thermoplastic resin film layer is peeled off.

<Evaluation of uneven shape of decorative resin molded products>
Regarding the change in the shape of the unevenness before and after manufacturing the decorative resin molded product from each decorative sheet, the feeling of unevenness was evaluated visually and by touch. The evaluation criteria are as follows. The results are shown in Tables 1A and 2A.
〇: There is almost no change in the unevenness even after the decorative resin molded product, and the unevenness is strongly felt.
Δ: The unevenness changed after the decorative resin molded product, but the decorative resin molded product also has an uneven feeling.
X: After the decorative resin molded product is formed, the unevenness is greatly changed, and the decorative resin molded product does not have the unevenness.

EB1
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 95 parts by mass tetrafunctional urethane acrylate oligomer (weight average molecular weight; 6,000): 5 parts by mass
EB2
Bifunctional Polycarbonate Acrylate (Weight Average Molecular Weight; 8,000): 95 parts by mass Bifunctional Silicone Acrylate Oligomer (Weight Average Molecular Weight; 6,000): 5 parts by mass
EB3
Trifunctional pentaerythritol acrylate (weight average molecular weight; 300): 30 parts by mass Acrylic polymer (weight average molecular weight 120,000): 70 parts by mass
UV
Urethane-based acrylate oligomer (weight average molecular weight: about 8000): 20 parts by mass Bifunctional acrylate monomer: 60 parts by mass Photosensitive compound: 5 parts by mass Photopolymerization initiator: 5 parts by mass Filler and pigment: 10 parts by mass
Polyester resin composition of adhesive layer Polyester polyol: isocyanate = 100:10
Extruded polyethylene <br /> Extruded grade low density PE
Heat-laminated polyethylene film <br /> Low-density PE film

In Example 7A, the thermoplastic resin film is extruded directly onto the resin layer made of the partially exposed acrylic resin film (thermoplastic resin), but the evaluation of the uneven shape of the decorative resin molded product is excellent. rice field. From this result, the unevenness of the decorative resin molded product was dominated by the shape of the surface layer (rise layer) made of the curable resin, and the acrylic resin film was slightly deformed during extrusion molding. Even so, it is considered that the unevenness does not deteriorate as long as the surface layer is not deformed.

Example 9A
Substrate layer / picture layer / primer layer / surface layer having uneven shape / thermoplastic resin in the same manner as in Example 1A except that A-PET was used for extrusion molding on the surface layer instead of polyethylene. A decorative sheet having a laminated structure in which film layers (A-PET films) were laminated in order was obtained. When a decorative resin molded product was produced using the obtained decorative sheet in the same manner as in other examples, the three-dimensional moldability was good, and both the decorative sheet and the decorative resin molded product had a surface surface. I felt a feeling of unevenness. Further, in Example 1A, a slight gate flow was generated in some places, but it was not confirmed in Example 9A. Further, in Example 1A, a residue of the thermoplastic resin film was observed in the suction holes of the female mold after molding, but it was not confirmed in Example 9A.

Example 10A
As the ionizing radiation curable resin composition forming the surface layer, EB2 was used instead of EB1 (however, it was applied so that the thickness after curing was 30 μm) in the same manner as in Example 1A. , A decorative sheet having a laminated structure in which a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape / a thermoplastic resin film layer were laminated in this order was obtained. In the same manner as in Examples 1A to 8A, the uneven shape of the decorative sheet and the decorative resin molded product was evaluated. The results are shown in Table 3A. In Examples 1A to 8A, the surface layer was not cracked even by vacuum forming the decorative sheet at the time of the evaluation, but in Example 10A, the thickness of the surface layer was as thick as 30 μm. , The surface layer was slightly cracked by molding.

Example 11A
As the ionizing radiation curable resin composition forming the surface layer, EB2 was used instead of EB1 (however, it was applied so that the thickness after curing was 50 μm) in the same manner as in Example 1A. , A decorative sheet having a laminated structure in which a base material layer / a pattern layer / a primer layer / a surface layer having an uneven shape / a thermoplastic resin film layer were laminated in this order was obtained. In the same manner as in Examples 1A to 8A, the uneven shape of the decorative sheet and the decorative resin molded product was evaluated. The results are shown in Table 3A. In Examples 1A to 8A, the surface layer was not cracked even by vacuum forming the decorative sheet at the time of the evaluation, but in Example 11A, the surface layer was thick, so that the surface layer was formed by molding. The surface layer was cracked.

[Manufacturing of decorative sheets]
Example 1B
An ABS resin film (thickness 200 μm) was used as the base material layer. A wood grain pattern layer (thickness 5 μm) was formed by gravure printing on the base material layer using an ink composition containing an acrylic resin. A resin composition for a primer layer containing a binder resin composed of a two-component curable resin containing 100 parts of a main agent (acrylic polyol / urethane, mass ratio 9/1) and 7 parts of a curing agent (hexamethylene diisocyanate) on the pattern layer. It was applied and dried to form a primer layer having a thickness of 2 μm, and a laminate in which a base material layer / a pattern layer / a primer layer was laminated in this order was obtained.

The primer layer side of the laminate obtained above was embossed to form a dot-patterned uneven shape on the primer layer. The embossing plate depth (height from the bottom of the concave portion to the upper surface of the convex portion) of the embossed plate used for the embossing is 60 μm. Next, the ionizing radiation curable resin composition (EB1) described later was applied onto the primer layer on which the uneven shape was formed so that the thickness after curing was 8 μm. This resin composition was cured by irradiating the resin composition with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) to form a surface layer having an uneven shape.

Next, an adhesive made of a polyester resin composition was applied onto the surface layer so that the thickness after curing was 30 μm, and the adhesive layer was formed so as to fill the uneven concave portions of the surface layer. .. Next, a release film layer (thickness 30 μm) formed of polyethylene is laminated on the adhesive layer, and a base material layer / pattern layer / primer layer / surface layer having an uneven shape / unevenness protective layer (adhesive layer / A decorative sheet having a laminated structure in which the release film layers) were laminated in order was obtained.

Example 2B
An acrylic resin film (thickness 75 μm) was used as the surface layer. A wood grain pattern layer (thickness 5 μm) was formed on the surface layer by gravure printing using an ink composition containing an acrylic resin. An ABS resin film (thickness 200 μm) as a base material layer was laminated on the pattern layer. Next, the surface layer side of the obtained laminate was embossed to form a dot-patterned uneven shape on the surface layer. The embossed plate used for embossing is the same as in Example 1B. From the above, a laminated body in which the base material layer / the pattern layer / the surface layer having the uneven shape was laminated in order was obtained. Next, in the same manner as in Example 1B, an adhesive layer and a release film are laminated on the surface layer, and a base material layer / a pattern layer / a surface layer having an uneven shape / an unevenness protective layer (adhesive layer / release film layer). ) Are laminated in order to obtain a decorative sheet having a laminated structure.

Example 3B
In the same manner as in Example 1B, after obtaining a laminate in which the base material layer / pattern layer / primer layer are laminated in this order, the ionizing radiation curable resin composition (EB2) described later is used to have an uneven shape. A surface layer was formed. On the other hand, the ionizing radiation curable resin composition (EB3) described later was applied onto the surface layer so that the thickness after curing was 10 μm. This resin composition was irradiated with an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) to cure it, and a release layer was formed on the surface layer.

Next, an adhesive made of a polyester resin composition is applied onto the release layer so that the thickness after curing is 30 μm, and the adhesive layer is formed by filling the uneven concave portions of the surface layer. bottom. Next, the above-mentioned release film layer is laminated from the adhesive layer side on the adhesive layer, and the base material layer / pattern layer / primer layer / surface layer having uneven shape / uneven protection layer (release layer / adhesion). A decorative sheet having a laminated structure in which layers / release film layers) were laminated in order was obtained.

Comparative Example 1B
Substrate layer / picture layer / surface layer having uneven shape / uneven protection layer (polyethylene layer) in the same manner as in Example 2B except that the polyethylene layer was formed by extrusion molding on the surface layer having the uneven shape. ) Are laminated in order to obtain a decorative sheet having a laminated structure. As the conditions for extrusion molding, the temperature under the die of the extruder was 230 to 250 ° C., and the thickness of the polyethylene layer was 50 μm.

Comparative Example 2B
A polyethylene film (thickness 50 μm) was laminated on a surface layer having an uneven shape, and a base layer / A decorative sheet having a laminated structure in which a pattern layer / a primer layer / a surface layer having an uneven shape / an uneven protective layer (polyethylene film layer) was laminated in this order was obtained. The conditions of the heat lamination method were a heating temperature of 200 to 230 ° C. and a pressure of 5 kgf / cm ² .

[Manufacturing of decorative resin molded products]
Each decorative sheet was heated to 160 ° C. with an infrared heater to soften it. Next, vacuum forming was performed using a vacuum forming mold (maximum draw ratio 100%), and premolding was performed so as to follow the internal shape of the mold and the mold was compacted. Then, a mixed resin of polycarbonate and ABS was injected into the cavity of the mold, and the decorative sheet and the molding resin were integrally molded to obtain a decorative resin molded product with a concavo-convex protective layer. Next, the concavo-convex protective layer was manually peeled off from the obtained decorative resin molded product with the concavo-convex protective layer to obtain a decorative resin molded product.

<Evaluation of uneven shape>
In order to evaluate the uneven shape of the surface of the decorative resin molded product, a surface roughness / contour shape measuring machine (Hardy Surf E-35A manufactured by Tokyo Seimitsu Co., Ltd.) was used, and the center line average roughness (Ra) was maximum. Height (Rmax) and ten-point average height (Rz) were measured. The results are shown in Table 1B.

<Evaluation of uneven shape of decorative sheet>
In the manufacturing process of the decorative sheet of Examples and Comparative Examples, the unevenness was visually and touch-evaluated with respect to the change in the unevenness shape of the surface layer before and after forming the unevenness protective layer. The unevenness protective layer was peeled off from the decorative sheet by manually peeling the unevenness protective layer from the decorative sheet. The evaluation criteria are as follows. The results are shown in Table 1B.
〇: There was almost no change in the unevenness.
Δ: The feeling of unevenness changed slightly.
X: The unevenness was greatly changed, and the unevenness was not felt.

<Evaluation of uneven shape of decorative resin molded products>
Regarding the change in the shape of the unevenness before and after manufacturing the decorative resin molded product from each decorative sheet, the feeling of unevenness was evaluated visually and by touch. The evaluation criteria are as follows. The results are shown in Table 1B. 〇: There was almost no change in the unevenness even after the decorative resin molded product, and the unevenness was strongly felt.
Δ: The unevenness was slightly changed after the product was made into a decorative resin molded product.
X: After the product was made of a decorative resin, the unevenness was significantly changed, and the unevenness was not felt.

In Table 1B, "-" indicates that no measurement was performed.

EB1
Bifunctional polycarbonate acrylate (weight average molecular weight; 10,000): 95 parts by mass tetrafunctional urethane acrylate oligomer (weight average molecular weight; 6,000): 5 parts by mass
EB2
Bifunctional Polycarbonate Acrylate (Weight Average Molecular Weight; 8,000): 95 parts by mass Bifunctional Silicone Acrylate Oligomer (Weight Average Molecular Weight; 6,000): 5 parts by mass
EB3
Trifunctional pentaerythritol acrylate (weight average molecular weight; 300): 30 parts by mass Acrylic polymer (weight average molecular weight 120,000): 70 parts by mass
Polyester resin composition of adhesive layer Polyester polyol: isocyanate = 100:10
Polyethylene extruded in Comparative Example 1B Extruded grade low density PE
Polyethylene film heat-laminated in Comparative Example 2B Low-density PE film

1 Base material layer 2 Surface layer 3 Concavo-convex protection layer 4 Primer layer 5 Pattern layer 6 Transparent resin layer 7 Resin layer 8 Molding resin layer 30 Thermoplastic resin film layer 31 Adhesive layer 32 Release layer 33 Release film layer 34 Adhesive layer

Claims (1)

A decorative sheet in which at least a base material layer, a surface layer formed of a cured product of a curable resin composition and having an uneven shape, and a removable thermoplastic resin film layer are laminated in this order.

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